Next Article in Journal
Tart Cherry Juice and Seeds Affect Pro-Inflammatory Markers in Visceral Adipose Tissue of High-Fat Diet Obese Rats
Next Article in Special Issue
Towards Enhanced MRI Performance of Tumor-Specific Dimeric Phenylboronic Contrast Agents
Previous Article in Journal
Novel Fast Chromatography-Tandem Mass Spectrometric Quantitative Approach for the Determination of Plant-Extracted Phytosterols and Tocopherols
Previous Article in Special Issue
Synthesis of Bis(Carboranyl)amides 1,1′-μ-(CH2NH(O)C(CH2)n-1,2-C2B10H11)2 (n = 0, 1) and Attempt of Synthesis of Gadolinium Bis(Dicarbollide)
 
 
Search for Articles:
Title / Keyword
Author / Affiliation / Email
Journal
Article Type
 
 
Advanced Search
 
Section
Special Issue
Volume
Issue
Number
Page
 
Journals
Molecules
Volume 26
Issue 5
10.3390/molecules26051401
molecules-logo
Submit to this Journal Review for this Journal Propose a Special Issue
► Article Menu

Article Menu

share Share announcement Help format_quote Cite question_answer Discuss in SciProfiles thumb_up
...
Endorse textsms
...
Comment
first_page
settings
Order Article Reprints
Font Type:
Arial Georgia Verdana
Font Size:
Aa Aa Aa
Line Spacing:
Column Width:
Background:
Review

Recent Progress on Synthesis of N,N′-Chelate Organoboron Derivatives

by
Tianbao Yang
,
Niu Tang
,
Qizhong Wan
*,
Shuang-Feng Yin
and
Renhua Qiu
*
State Key Laboratory of Chemo/Biosensing and Chemometrics, Advanced Catalytic Engineering Research Center of the Ministry of Education, College of Chemistry and Chemical Engineering, Institute of Shenzhen, Hunan University, Changsha 410082, China
*
Authors to whom correspondence should be addressed.
Molecules 2021, 26(5), 1401; https://doi.org/10.3390/molecules26051401
Submission received: 7 February 2021 / Revised: 26 February 2021 / Accepted: 1 March 2021 / Published: 5 March 2021
(This article belongs to the Special Issue Synthesis and Application of Organoboron Derivatives)
Browse Figures
Versions Notes

Abstract

:
N,N′-chelate organoboron compounds have been successfully applied in bioimaging, organic light-emitting diodes (OLEDs), functional polymer, photocatalyst, electroluminescent (EL) devices, and other science and technology areas. However, the concise and efficient synthetic methods become more and more significant for material science, biomedical research, or other practical science. Here, we summarized the organoboron-N,N′-chelate derivatives and showed the different routes of their syntheses. Traditional methods to synthesize N,N′-chelate organoboron compounds were mainly using bidentate ligand containing nitrogen reacting with trivalent boron reagents. In this review, we described a series of bidentate ligands, such as bipyridine, 2-(pyridin-2-yl)-1H-indole, 2-(5-methyl-1H-pyrrol-2-yl)quinoline, N-(quinolin-8-yl)acetamide, 1,10-phenanthroline, and diketopyrrolopyrrole (DPP).

1. Introduction

N,N′-chelate tetracoordinated organoboron compounds have been widely applied in various science and technology areas. For example, boron dipyrromethene derivatives (BODIPY) were developed in luminescent materials [1,2,3,4,5], dyes [6,7,8,9], photosensitizers [10,11,12,13,14], molecular switches [15,16,17], photodynamic therapy [18,19,20,21,22], molecular probes [23,24,25,26], and bioimaging [27,28,29]. In recent decades, N,N′-chelate compounds become a popular topic and have gradually attracted the attention of scientists. Four-coordinated organoboron compounds (BAr2 (N, N)) have interesting luminescent properties that can be modulated by various substituents in the N, N′-chelating framework [30]. More and more similar structures were explored and exhibited wonderful results in fluorescent materials [30,31], cell bioimaging (A1) [32], organic light-emitting diodes (OLEDs) (A2) [33], functional polymer (A3) [34], photocatalyst (A8) [35], electroluminescent (EL) devices [36], and so on, as shown in Figure 1. Herein, various traditional methods for the formation of N,N′-chelate tetracoordinated organoboron complexes were exhibited in this review. The main highlights include that (a) the diversified synthetic methods were provided, (b) readily available trivalent boron compounds were used as boron reagents, (c) various complex starting materials were designed as good bidentate ligands, and (d) these reactions showed a wide range of tetracoordinated organoboron complexes and excellent optical properties. In this paper, we made a conclusion of all articles of the corresponding organic synthetic routes.
In recent years, the research on their syntheses falls into the following categories. At first, bipyridine derivatives could be used as bidentate ligand reacting with triphenylboron to form the desired products, as shown in Figure 2. The second, an indole connecting with pyridine derivatives (or other nitrogen heterocyclic molecule) reacted with triphenylboron to obtain the corresponding compounds, as shown in Figure 2. The third, pyridine attaching on pyrrole derivatives (or other nitrogen heterocyclic molecule) and trivalent boron could produce the fluorescent organoboron compounds, as shown in Figure 2. The fourth, a quinoline linking with pyrrole derivatives (or other nitrogen heterocyclic molecule) has been reported as a bidentate ligand to react with boron reagents. The different fluorescent compounds could be synthesized by N-(quinolin-8-yl)acetamide derivatives and boron reagents, as shown in Figure 2. The fifth, other bidentate ligands including 1,10-phenanthroline and diketopyrrolopyrrole (DPP) derivatives could also react with trivalent boron to obtain tetracoordinated organoboron compounds, as shown in Figure 2.

2. Bipyridine-Based Derivatives as Bidentate Ligand

In this section, different traditional methods for the formation of N,N′-chelate organoboron derivatives will be displayed in detail from the following aspects.

2.1. Bipyridine as Bidentate Ligand

In 1985, Heinrich Noeth and co-workers reported that dibutyl(((trifluoromethyl)sulfonyl)oxy)borane (1) reacted with bipyridine (2) to complete desired product. The solution of the diorganylborane should be cooled to −78 °C in this reaction. Bipyridine-dibutylboronium(1+) triflate (3) was confirmed by 11B NMR in their lab [37], as shown in Scheme 1. This protocol realized the synthesis of bipyridine coordinated organoboron complex at low temperature. It played a certain role in promoting the deep study of tetracoordinated organoboron compounds.

2.2. 2,5-Di(pyridin-2-yl)pyrazine and 2′, 2′: 4′, 4′: 2″, 2‴-Quaterpyridine as Bidentate Ligand

In 2002, Matthias Wagner’s group adopted ferrocenylboranes (4) to react with 2,5-bis(pyridyl)pyrazine (5) and 2′, 2′: 4′, 4′: 2″, 2‴-quaterpyridine (6) to obtain charge-transfer complexes, respectively [38]. The organoboron adducts possess green color, which is charge transfer from the electron-rich ferrocene skeleton to their electron-poor aromatic structures, as shown in Scheme 2. This strategy provided a new route to acquire more ferrocenylborane derivatives with high yield and simple operation.

2.3. Bipyridine in {Fc(Bbipy)2O}(PF6) and {Fc(Bbipy}2(OH)2}(PF6)

In 2002, Matthias Wagner’s group studied the synthesis of ferrocene complexes {Fc(Bbipy)2O}(PF6)2 (11) and {Fc(Bbipy)2(OH)2}(PF6)2 (12) [39,40], as shown in Scheme 3. They successfully synthesized tetracoordinated organoboron compounds with two boron centers. All of these compounds have the property of charge transfer. They could realize ring-closing and ring-opening products using bromide (FcMeBr) for the formation of 11 and 12 by adding different amounts of water in the reaction.

2.4. 4,4′-Di(but-3-en-1-yl)-2,2′-bipyridine as Bidentate Ligand

In 2005, Matthias Wagner’s team reported other N,N′-chelate organoboron complexes in this reaction. They used dibromo(phenyl)borane, bromo(methyl)(phenyl)borane, bromo(ethoxy)(phenyl)borane to give bipyridine adducts with satisfactory yields (15–18, 76–89%) [41], as shown in Scheme 4. This reaction indicated that different N,N′-chelate organoboron compounds could be obtained by adding distinct boron reagents under ambient temperature.

2.5. Bipyridine Reacting with 5-Chloro-5,10-dihydrodibenzo[b,e]borinine

In 2009, Warren E. Piers’s lab prepared a series of neutral radicals, which had significant spin density on boron [42]. The scaffold of 2,2′-bipyridyl-stabilized boronium ions was interesting and demonstrated bipyridine adducts persistent neutral radical. They added AgBF4 in this reaction and offered moderate yields (20–23, yield 53–77%), as shown in Scheme 5. It was proved that this protocol could easily get the target 2,2′-bipyridyl boronium ions and neutral radicals.

2.6. Bipyridine for the Formation of N,N′-Chelate Organoboron and Ferrocene Derivatives

In 2010, Matthias Wagner’s group reported a more powerful synthetic route of ferrocene complexes [43]. They used bromide (26) to obtain FcBBr polymers (27, 28) and continued to form the bipyridine organoboron polymers with main chain charge-transfer structure (30, 32, 33, 80%, 65%, 76%), as shown in Scheme 6. This method provided a new opportunity for the synthesis of multifunctional organoboron polymers.

2.7. Bipyridine Reacting with 5-Bromo-10-mesityl-5,10-dihydroboranthrene

In 2011, Matthias Wagner’s group has been committed to the development of more diversified N,N′-chelate organoboron chemistry for many years [44]. It always showed wonderful results in bipyridine organoboron adducts. They realized cleavage of the B-O-B bridge in this reaction and got the desired product with moderate yield (36, 51%), as shown in Scheme 7. In this protocol, they prepared 5-bromo-10-mesityl-5,10-dihydroboranthrene (35) as a boron reagent. This building block revealed a novel synthetic route for us.

3. Indole-Based Derivatives as Bidentate Ligand

3.1. 2-(Pyridin-2-yl)-1H-indole and 2-(Pyridin-2-yl)-1H-pyrrolo[2,3-b]pyridine

Bipyridine organoboron adducts have been synthesized using various boron reagents. Except for bipyridine as bidentate ligand, indole skeleton was chosen viably. In 2000, Suning Wang’s group has synthesized and characterized blue/green luminescent materials, diphenylboron complex (38, 65%), and complex (40, 71%) [36], as shown in Scheme 8. 2-(pyridin-2-yl)-1H-indole and 2-(pyridin-2-yl)-1H-pyrrolo[2,3-b]pyridine reacted with commercially available triphenylboron to prepare the target products. The complex (40) has been developed to function as the light-emitting layer.

3.2. 2-(Pyridin-2-yl)-1H-indole Derivatives Reacting with BPh3

In 2002, Suning Wang’s group explored more 5-substituted diphenylboron complexes. In this case, 5-fluoro-2-(pyridin-2-yl)-1H-indole, 5-chloro-2-(pyridin-2-yl)-1H-indole, and 5-methoxy-2-(pyridin-2-yl)-1H-indole could get desired products (42–44) [45], as shown in Scheme 9. They examined the effect of blue shift to 490 and 487 nm (42, 43, -F, -Cl) and red shift to 532 nm (44, -OCH3), respectively. They found that compound 42 could be applied in an electroluminescent device as the emitter and the electron transport material. It was inferred that different substituted groups could tune the luminescence and the property of electroluminescence of N,N′-chelate organoboron compounds.

3.3. 2-(1H-Indol-2-yl)thiazole, 8-(1H-Benzo[d]imidazol-2-yl)Quinoline and Their Derivatives

In 2005, Suning Wang’s group continued to present different indole skeleton bidentate ligands. Substituted-2-(pyridin-2-yl)-1H-indole (45), 2-(pyridin-2-yl)-1H-benzo[d]imidazole (46), 2-(1H-indol-2-yl)thiazole (47), 1-(1H-benzo[d]imidazol-2-yl)isoquinoline (48, X = C), 1-(3H-imidazo[4,5-b]pyridin-2-yl)isoquinoline (48, X = N) began with triphenylboron to generate N,N′ chelate boron complexes (49–56, 59–78%) from blue to red [30], as shown in Scheme 10. They also found that these complexes could be applied in not only emitters but also electron transport materials of electroluminescent (EL) equipment.

3.4. 2-(Pyridin-2-yl)-1H-indole Reacting with FcBMeBr

In 2005, Matthias Wagner’s group achieved reaction of ferrocene bromide and 2-(pyridin-2-yl)-1H-indole sodium to give rise to the formation of FcBMe(5-F-bipyridine) (58, 51%) and Fc2B(5-F-bipyridine) (59, 23%) in acceptable yields [46], as shown in Scheme 11. It indicated that N,N′-chelate organoboron compounds containing multiple metals could be obtained by making use of this simple protocol.

3.5. 2-(1H-Indol-7-yl)benzo[d]oxazole, 2-(1H-Indol-7-yl)benzo[d]thiazole, and 2-(1H-Indol-7-yl)-1-octyl-1H-benzo[d]imidazole

In 2016, David Curiel’s group described a reaction of 2-(1H-indol-7-yl)benzo[d]oxazole (60), 2-(1H-indol-7-yl)benzo[d]thiazole (61), and 2-(1H-indol-7-yl)-1-octyl-1H-benzo[d]imidazole (62) to generate organoboron complexes (63–65) with tuned emission and cell bioimaging utility [32], as shown in Scheme 12. To synthesize these diphenylboron complexes, they choose triphenylboron as boron reagent. In this paper, they succeeded in introducing more heteroatoms (S, O, N) in this building block.

4. Pyridine-Based Derivatives as Bidentate Ligand

4.1. 2-(1H-Pyrazol-5-yl)pyridine Reacting with BPh3

In 2003, Yun Chi’s group reported a reaction of 2-(1H-pyrazol-5-yl)pyridine derivatives (67) and triphenylboron to produce pyridyl pyrazolate boron complexes (68–73, 48–90%) [47], as shown in Scheme 13, which exhibited the ability of remarkable dual fluorescence through the photoinduced electron transfer reaction. In this system, it was more efficient to synthesize the N,N′-chelate organoboron adducts in tetrahydrofuran (THF) solution for one hour. They found that electron-deficient B(C6F5)3 reagent could be also feasible in this reaction.

4.2. Pyridin-2-ylmethanamine Reacting with Hydroxydiphenylborane

In 2005, Noemí Andrade-López’s group provided another method to complete the N-8-(diphenyl-hydroxy-2-aminomethylpyridine)borane (76, 95%) with high yield when added 2-pyridylmethylamine (74) and diphenylborinic acid (75) together [48], as shown in Scheme 14. In this case, they used air-stable boron reagent (diphenylborinic acid). It was proved that nonrigid bidentate ligand 2-pyridylmethylamine could also be activated.

4.3. 2-(1H-Pyrazol-5-yl)pyridine Analogs Reacting with BPh3

In 2006, Yun Chi’s group developed 2-(1H-pyrazol-5-yl)pyridine derivatives (77) to acquire organoboron compound (78) [49], as shown in Scheme 15. It was interesting that the authors succeeded in introducing crown ether structure for detecting the alkali or alkaline earth ions.

4.4. 2-(4H-1,2,4-Triazol-3-yl)pyridine Derivatives Reacting with BPh3

In 2014, Wesley R. Browne’s group showed the resulting pyridyl-1,2,4-triazole tetracoordinate organoboron complexes as available and controllable blue emitters [50]. In this system, they could only obtain the N1-bound isomer (80–83), while N3-bound isomer was not found (84), as shown in Scheme 16. It was inferred that the boron atom of triphenylboron preferred to attacking with N1 atom center. The emission quantum yield of the complex (80) was up to 0.72. Synthesized compounds displayed a great range of emissions from 397 nm to 494 nm.

4.5. 2-(3,5-Bis(trifluoromethyl)-1H-pyrrol-2-yl)pyridine as Bidentate Ligand

In 2016, Yun Chi’s group provided a method for the synthesis of pyridyl pyrrolide boron complexes (88–90, 41–48%), which could be developed to function as organic light-emitting diodes (OLEDs) [33], as described in Scheme 17. This building block connected the electron-donating portion with the electron-accepting moieties together and succeed in generating external quantum efficiency (EQE) of 13.5%. 2-(3,5-bis(trifluoromethyl)-1H-pyrrol-2-yl)pyridine (85) and boron trichloride resulted in the intermediate compound (86, 57%). Next, it reacts with Grignard reagent (87) to give the final organoboron products (88–90). This protocol used the easy availability of Grignard reagent to produce pyridyl pyrrolide boron complexes.

4.6. 2-(5-Methyl-1H-pyrrol-2-yl)pyridine, 2-(Pyridin-2-yl)-1H-Indole, and (Z)-2-(Phenyl(2H-pyrrol-2-ylidene)methyl)-1H-pyrrole as Bidentate Ligand

In 2017, Kee-In Lee’s group reported a synthetic route for the generation of N,N′-chelate organoboron complexes with mild condition and easy operation in moderate yields [51]. In this strategy, they added general phenylboronic acids to react with ligands using widely available K3PO4 to form desired products (93–96, 72–79%), as shown in Scheme 18. In this case, 2-(5-methyl-1H-pyrrol-2-yl)pyridine, 2-(pyridin-2-yl)-1H-indole, and (Z)-2-(phenyl(2H-pyrrol-2-ylidene)methyl)-1H-pyrrole could be able to respond smoothly.

5. Quinoline-Based Derivatives as Bidentate Ligand

5.1. 2-(5-Methyl-1H-pyrrol-2-yl)quinoline and 2-(5-Methyl-1H-pyrrol-2-yl)quinoxaline as Bidentate Ligand

In 2005, Chin-Ti Chen’s group exploited 2-(5-methyl-1H-pyrrol-2-yl)pyridine (97), 2-(5-methyl-1H-pyrrol-2-yl)quinoline (98), and 2-(5-methyl-1H-pyrrol-2-yl)quinoxaline (99) reacting with triphenylboron to afford diphenylboron complexes (100–102, 63–89%) [52], as shown in Scheme 19. The complexes [(pyro)BPh2] (100), [(noro)BPh2] (101), and [(xaro)BPh2] (102) exhibited emission peak maxima of strong photoluminescence at different locations such as 490 nm, 510 nm and 575 nm, respectively. The research group adopted quinoline linked with pyrrole in one molecule as bidentate ligand to react with triphenylboron.

5.2. 2-(1H-Benzo[d]Imidazol-2-yl)quinoline and 2-(Quinolin-2-yl)-1H-naphtho[2,3-d]Imidazole Served as Bidentate Ligand

In 2006, Tsun-Ren Chen’s group realized 2-(1H-benzo[d]imidazol-2-yl)quinoline (103) and 2-(quinolin-2-yl)-1H-naphtho[2,3-d]imidazole (104) reacting with triphenylboron to generate diphenylboron complexes (105–106, 30–35%) [53], as shown in Scheme 20. The product (105) could be used as organometallic emitting material in organic light-emitting diodes (OLEDs). They succeeded in the synthesis of target organoboron products and adopted them (105, 106) as the emitting materials of electroluminescence (EL) device. It was demonstrated that tetracoordinated organoboron complexes could be selected as organic light-emitting diodes (OLEDs) as well.

5.3. 1-(3-(Trifluoromethyl)-1H-pyrazol-5-yl)isoquinoline as Bidentate Ligand

Recently, in 2019, Pi-Tai Chou’s group designed and synthesized 1-isoquinolinyl pyrazolate biphenylboron complexes [54]. 1-(3-(trifluoromethyl)-1H-pyrazol-5-yl)isoquinoline was used to react with various boron reagents (BPh3, BCl3, 9-bromo-9-borafluorene, or 10-bromo-9-oxa-10-boraanthracene) to afford desired products (107–111), as shown in Scheme 21. The authors measured the time-resolved fluorescence and studied theoretical calculation, then found these complexes having the phenomenon of photoinduced electron transfer (PET) from the locally excited (LE) (over the isoquinolinyl pyrazolate moiety) to charge transfer (CT) states (from isoquinolinyl to aryl appendages).

5.4. N-(Quinolin-8-yl)acetamide as Bidentate Ligand

In 2008, Yoshiki Chujo’s group prepared N,N′-chelate tetracoordinated organoboron polymers by Sonogashira-Hagihara cross-coupling reaction [34]. They reported a reaction of N-(quinolin-8-yl)acetamide (112) and triphenylboron (43%), as shown in Scheme 22. The research group used tri(4-iodinephenyl)boron to synthesize the monomer (114, 53%). It continued to react with alkynes to obtain the final polymers (115–117, 40–51%). This paper showed that the π-conjugated linker unit had a great influence on the fluorescent quantum efficiencies of the synthesized polymers. Besides, they also observed an obvious energy transfer.

5.5. (S)-N-(1-((5-Iodoquinolin-8-yl)amino)-1-oxopropan-2-yl)hexanamide as Bidentate Ligand

In 2010, Yoshiki Chujo’s group used (S)-N-(1-((5-iodoquinolin-8-yl)amino)-1-oxopropan-2-yl)hexanamide (118) and diphenyl with two boronbromide centers resulting in organoboron monomer (120, 24%) [55], as shown in Scheme 23. They chose palladium-catalyzed Sonogashira coupling between iodide (120) and bis-alkyne to prepare luminescent chiral four-coordination organoboron quinoline-based polymers. It was interesting to see that the quantum yield (ΦF) of the synthesized polymer (122) was up to 0.8.

5.6. N-(5-Iodoquinolin-8-yl)undecanamide as Bidentate Ligand

In 2010, Yoshiki Chujo’s group developed strong luminescent organoboron polymers connected with bifunctional 8-aminoquinolate linkers [56]. They used N-(5-iodoquinolin-8-yl)undecanamide and bis-alkyne resulting in corresponding polymers (124–127) by Sonogashira-Hagihara cross-coupling reaction, as shown in Scheme 24. In this case, they introduced long alkyl chains and various aryl groups and finally found the organoboron polymer (127, Ar1 = P, Ar2 = F, 85%) (ΦF = 0.65) achieving a higher quantum yield than others. Compared with (S)-N-(1-((5-iodoquinolin-8-yl)amino)-1-oxopropan-2-yl)hexanamide as starting material to obtain N,N′-chelate organoboron complexes, N-(5-iodoquinolin-8-yl)undecanamide as bidentate ligand showed different optical properties. It indicated that the fluorescent characteristic of organoboron polymers could be changed by different substituted portions.

5.7. N-(quinolin-8-yl)acetamide as Bidentate Ligand

Two years later, in 2012, Yoshiki Chujo’s group designed and synthesized 8-aminoquinolate-based organoboron polymers with rigid structure, which had electron-donating and electron-accepting structure in the basic skeleton [57]. In order to get the corresponding starting material, they added tin compound (128) and boron tribromide to give the intermediate (130) in two steps, as shown in Scheme 25. Next, it continued to react with N-(quinolin-8-yl)acetamide to afford adduct monomer in acceptable yield (131, 34%). Final 8-aminoquinolate-based organoboron products were prepared by classical Sonogashira-Hagihara cross-coupling reaction (132, 133, 84%, 84%). The quantum yield of polymer (132) was up to 0.53. It was certain that this scaffold with 8-aminoquinolate-based could achieve more efficient luminescent properties by introducing the -C8F17 group.

5.8. Quinolin-8-amine as Bidentate Ligand

In 2012, Douglas W. Stephan’s group reported a reaction of readily available quinoline-8-amine (134) and electron-deficient B(C6F5)2H [58]. Biperfluorophenylboron complex was synthesized in moderate yield (135, 76%) without any catalyst, as shown in Scheme 26. The result indicated that tetracoordinated organoboron compounds could also be successfully obtained from primary amines.

5.9. 3-Phenyl-N-(quinolin-8-yl)propanamide Derivatives as Bidentate Ligand

In 2020, Xu’s group designed and synthesized a series of 3-phenyl-N-(quinolin-8-yl)propanamide-based organoboron complexes as photocatalysts [35]. At first, they prepared starting materials 3-phenyl-N-(quinolin-8-yl)propanamide derivatives (136) that were added in Mn/p-tosyl chloride/Na2CO3 system. Desired 3-phenyl-N-(quinolin-8-yl)propanamide-based organoboron complexes were acquired with high yields (138–144, 80–96%), as shown in Scheme 27. In this case, they added cheap transitional metal manganese powder. It was worth noting that they used widely available and air-stable boron reagents (Ar-BF3K, 137). This protocol provided a useful path for the generation of aminoquinolate-based organoboron complexes efficiently.

5.10. 2,2,2-Trifluoro-N-(quinolin-8-yl)acetamide Derivatives as Bidentate Ligand

In 2020, our group almost at the same time reported the reaction of 2,2,2-trifluoro-N-(quinolin-8-yl)acetamide derivatives (145) and sodium tetraarylborate, resulting in aminoquinolate-based organoboron complexes (146–168) with high yields using iodine as catalyst [31], as depicted in Scheme 28. We made a modification from 2,2,2-trifluoro-N-(quinolin-8-yl)acetamide with various functional groups. In our protocol, we synthesized successfully a series of cheap and air-stable sodium tetraarylborates. Only a catalytic amount of iodine was enough to drive this reaction. In addition, we showed that adding external acids in this system formed the novel N,N′-chelate organoboron aminoquinolate with moderate yields (159–168, 45–89%). All the complexes were fully characterized and we found that the quantum yield of organoboron compound (146) reached 0.79 when dissolved in dichloromethane.

6. 1,10-Phenanthroline and Others as Bidentate Ligand

6.1. 1,10-Phenanthroline as Bidentate Ligand

In 2013, Douglas W. Stephan’s group treated 1,10-phenanthroline with the same amount of the boron reagent B(C6F5)3 to afford the desired salt (170, 73%) under H2 (4 atm) condition [59], as shown in Scheme 29. The authors tried to develop an organoboron catalyst, which has the ability of frustrated Lewis pairs (FLPs) catalyst in practical applications. In this paper, they developed a new synthetic route of tetracoordinated organoboron complexes by using 1,10-phenanthroline.

6.2. 1,10-Phenanthroline as Bidentate Ligand

In 2016, Hiroyuki Higuchi’s group also reported 1,10-phenanthroline as bidentate ligand to react with 9-borabicyclo[3.3.1]nonan-9-yl trifluoromethanesulfonate to obtain the organoboron complex (172, 30%) [60], as shown in Scheme 30. Next, it was reacted with potassium iodide solution to afford the corresponding salt (173, 13%). It was noteworthy that the synthesized complex (173) displayed photoinduced different color behavior in the solid-state after UV irradiation.

6.3. (9E,10E)-N9,N10-Bis(6-methylheptyl)phenanthrene-9,10-diimine as Bitentate Ligand

In 2017, Douglas W. Stephan’s group described an original synthetic strategy to give rise to (9E,10E)-N9,N10-bis(6-methylheptyl)phenanthrene-9,10-diimine-based organoboron complex (177), but only found the radical (177) measured by direct analysis in real time mass spectrometry (DART-MS) and electron paramagnetic resonance (EPR) signal [61], as shown in Scheme 31. They continued to improve and develop previous work and used HB(C6F5)2 reagent to react with bidentate ligand (174) to prepare frustrated Lewis pairs (FLPs) catalyst in this paper.

6.4. Diketopyrrolopyrrole (DPP) Derivatives as Bitentate Ligand

In 2014, Takaki Kanbara and co-workers disclosed a route for the generation of diketopyrrolopyrrole (DPP)-based diphenylboron complexes with moderate yields (184–186, 21–71%) [62], as shown in Scheme 32. In this case, diketopyrrolopyrrole derivatives were synthesized by using 5-substituted-picolinonitrile (179) and dibutyl succinate (180). Next, triphenylboron reacted with them to form the diphenylboron complexes (184–186). At last, the authors studied the corresponding theoretical calculation in their work, which indicated that the introduction of the coordinating boron element could lower the band gap.

6.5. Diketopyrrolopyrrole (DPP) Derivatives as Bitentate Ligand

In 2014, Takaki Kanbara and co-workers continued to improve this scaffold by introducing phenylacetylene derivatives [63], by palladium-catalyzed Sonogashira coupling. Synthesized diketopyrrolopyrrole-based diphenylboron complexes (187–188) showed red-shift of the location of wavelengths to a near-infrared region, as shown in Scheme 33. This was a good strategy to extend π-conjugation of diketopyrrolopyrrole-based diphenylboron complexes by linking with more rigid phenylethynyl groups, which reached red-shift in near-infrared region and achieved high quantum yields.

6.6. Reactivity of 1,2,3,4,5-Pentaphenyl-1H-borole with Isocyanates

In 2016, Caleb D. Martin’s group used 1,2,3,4,5-pentaphenyl-1H-borole (189) with isocyanates to generate a seven-membered ring (194) and it continued to react with another isocyanate to afford more complex organoboron products (195, 196, 74%, 77%, respectively) [64], as shown in Scheme 34. The boron atom of the complex (191) would attack the nitrogen atom in the presence of pyridine to form a new adduct (192, 95%).

7. Conclusions and Outlook

In summary, tetracoordinated organoboron compounds have been widely applied in cell imaging, organic light-emitting diodes (OLEDs), functional polymer, photocatalyst, electroluminescent (EL) devices, and other science and technology areas. N,N′-chelate diarylboron complexes have been successfully synthesized by using a series of bidentate ligands and diversified boron reagents. Bidentate ligands mainly consist of two parts by using bipyridine, indole, pyrrole, quinoline, isoquinoline, pyridine, 1H-benzo[d]imidazole, and others. The boron reagents mainly include triphenylboron, boron trichloride, boron tribromide, B(C6F5)3, HB(C6F5)2, hydroxydiphenylborane (Ph2BOH), phenylboronic acids, sodium tetraaylborate, and FcMeBr in this review. However, there is main focus including exploring wider substrates as bidentate ligand, more diversified boron reagents, simpler and greener reaction condition, and higher yields. Besides, this N,N′-chelate organoboron framework should be developed in these fields such as molecular probes, cell imaging, fluorescent dyes, OLEDs, and so on. We expect with continuous effort more efficient and greener methods for exploiting more powerful diphenylboron complexes.

Author Contributions

Conceptualization, Q.W. and R.Q.; writing—original draft preparation, T.Y., N.T., Q.W., and R.Q.; writing—review and editing, T.Y., S.-F.Y., Q.W., and R.Q.; visualization, S.-F.Y. and R.Q.; supervision, R.Q.; project administration, Q.W. and R.Q. All authors have read and agreed to the published version of the manuscript.

Funding

The authors thank the Natural Science Foundation of China (21878071, and 21971060), Natural Science Foundation of Changsha (kq2004008), Hu-Xiang High Talent in Hunan Province (2018RS3042), and the Recruitment Program of China (WQ20164300353) for financial support.

Institutional Review Board Statement

Not applicable.

Informed Consent Statement

Not applicable.

Data Availability Statement

The data presented in this study are openly available in references [1,2,3,4,5,6,7,8,9,10,11,12,13,14,15,16,17,18,19,20,21,22,23,24,25,26,27,28,29,30,31,32,33,34,35,36,37,38,39,40,41,42,43,44,45,46,47,48,49,50,51,52,53,54,55,56,57,58,59,60,61,62,63,64].

Acknowledgments

The authors thank Nobuaki Kambe (Osaka University), Wai-Yeung Wong (The Hong Kong Polytechnic University), and Chak-Tong Au (Hong Kong Baptist University) for helpful discussion.

Conflicts of Interest

The authors declare no conflict of interest.

References

  1. Maeda, C.; Nagahata, K.; Shirakawa, T.; Ema, T. Azahelicene-Fused BODIPY Analogues Showing Circularly Polarized Luminescence. Angew. Chem. Int. Ed. Engl. 2020, 59, 1–6. [Google Scholar] [CrossRef]
  2. Chi, W.; Chen, J.; Liu, W.; Wang, C.; Qi, Q.; Qiao, Q.; Tan, T.M.; Xiong, K.; Liu, X.; Kang, K.; et al. A General Descriptor DeltaE Enables the Quantitative Development of Luminescent Materials Based on Photoinduced Electron Transfer. J. Am. Chem. Soc. 2020, 142, 6777–6785. [Google Scholar] [CrossRef]
  3. Gartzia-Rivero, L.; Ray Leiva, C.; Sanchez-Carnerero, E.M.; Banuelos, J.; Moreno, F.; Maroto, B.L.; Garcia-Moreno, I.; Infantes, L.; Mendez, B.; Lopez-Arbeloa, I.; et al. Chiral Microneedles from an Achiral Bis(boron dipyrromethene): Spontaneous Mirror Symmetry Breaking Leading to a Promising Photoluminescent Organic Material. Langmuir 2019, 35, 5021–5028. [Google Scholar] [CrossRef] [PubMed]
  4. Tian, D.; Qi, F.; Ma, H.L.; Wang, X.Q.; Pan, Y.; Chen, R.F.; Shen, Z.; Liu, Z.P.; Huang, L.; Huang, W. Domino-like multi-emissions across red and near infrared from solid-state 2-/2,6-aryl substituted BODIPY dyes. Nat. Commun. 2018, 9, 2688. [Google Scholar] [CrossRef] [PubMed] [Green Version]
  5. Zhao, Y.; He, S.L.; Yang, J.Y.; Sun, H.; Shen, X.F.; Han, X.G.; Ni, Z.H. Study on TICT emission of TPE-BODIPY derivatives mediated by methyl group on BODIPY. Opt. Mater. 2018, 81, 102–108. [Google Scholar] [CrossRef]
  6. Li, G.; Hirano, T.; Yamada, K. Bright near-infrared chemiluminescent dyes: Phthalhydrazides conjugated with fluorescent BODIPYs. Dyes Pigm. 2020, 178, 108339. [Google Scholar] [CrossRef]
  7. Radunz, S.; Kraus, W.; Bischoff, F.A.; Emmerling, F.; Tschiche, H.R.; Resch-Genger, U. Temperature- and Structure-Dependent Optical Properties and Photophysics of BODIPY Dyes. J. Phys. Chem. A 2020, 124, 1787–1797. [Google Scholar] [CrossRef]
  8. Boens, N.; Verbelen, B.; Ortiz, M.J.; Jiao, L.; Dehaen, W. Synthesis of BODIPY dyes through postfunctionalization of the boron dipyrromethene core. Coord. Chem. Rev. 2019, 399, 213024. [Google Scholar] [CrossRef]
  9. Li, G.L.; Otsuka, Y.; Matsumiya, T.; Suzuki, T.; Li, J.Y.; Takahashi, M.; Yamada, K. A Straightforward Substitution Strategy to Tune BODIPY Dyes Spanning the Near-Infrared Region via Suzuki-Miyaura Cross-Coupling. Materials 2018, 11, 1297. [Google Scholar] [CrossRef] [PubMed] [Green Version]
  10. Cao, J.J.; Zhang, M.S.; Li, X.Q.; Yang, D.C.; Xu, G.; Liu, J.Y. A glutathione-responsive photosensitizer with fluorescence resonance energy transfer characteristics for imaging-guided targeting photodynamic therapy. Eur. J. Med. Chem. 2020, 193, 112203. [Google Scholar] [CrossRef] [PubMed]
  11. Lapok, L.; Cieslar, I.; Pedzinski, T.; Stadnicka, K.M.; Nowakowska, M. Near-Infrared Photoactive Aza-BODIPY: Thermally Robust and Photostable Photosensitizer and Efficient Electron Donor. Chemphyschem 2020, 21, 1–7. [Google Scholar] [CrossRef] [PubMed]
  12. Wang, C.J.; Qian, Y. A water soluble carbazolyl-BODIPY photosensitizer with orthogonal D-A structure for photodynamic therapy in living cells and zebrafish. Biomater. Sci. 2020, 8, 830–836. [Google Scholar] [CrossRef]
  13. Wang, C.J.; Qian, Y. A novel BODIPY-based photosensitizer with pH-active singlet oxygen generation for photodynamic therapy in lysosomes. Org. Biomol. Chem. 2019, 17, 8001–8007. [Google Scholar] [CrossRef]
  14. Wang, L.F.; Bai, J.; Qian, Y. Synthesis of a triphenylamine BODIPY photosensitizer with D–A configuration and its application in intracellular simulated photodynamic therapy. New J. Chem. 2019, 43, 16829–16834. [Google Scholar] [CrossRef]
  15. Dolati, H.; Haufe, L.C.; Denker, L.; Lorbach, A.; Grotjahn, R.; Horner, G.; Frank, R. Two pi-Electrons Make the Difference: From BODIPY to BODIIM Switchable Fluorescent Dyes. Chem. Eur. J. 2020, 26, 1422–1428. [Google Scholar] [CrossRef]
  16. Gautam, R.; Petritis, S.J.; Tomat, E. Redox-Switchable Cyan Fluorescence of a BODIPY Analog Inspired by Propentdyopent Pigments. Eur. J. Inorg. Chem. 2019, 2019, 68–72. [Google Scholar] [CrossRef]
  17. Shi, W.-J.; Huang, Y.; Liu, W.C.; Xu, D.; Chen, S.-T.; Liu, F.G.; Hu, J.Q.; Zheng, L.Y.; Chen, K. A BODIPY-based “OFF-ON” fluorescent probe for fast and selective detection of hypochlorite in living cells. Dyes Pigm. 2019, 170, 107566. [Google Scholar] [CrossRef]
  18. Nguyen, V.N.; Yim, Y.; Kim, S.; Ryu, B.; Swamy, K.M.K.; Kim, G.; Kwon, N.; Kim, C.Y.; Park, S.; Yoon, J. Molecular Design of Highly Efficient Heavy-Atom-Free Triplet BODIPY Derivatives for Photodynamic Therapy and Bioimaging. Angew. Chem. Int. Ed. Engl. 2020, 59, 8957–8962. [Google Scholar] [CrossRef] [PubMed]
  19. Pederzoli, M.; Wasif Baig, M.; Kyvala, M.; Pittner, J.; Cwiklik, L. Photophysics of BODIPY-Based Photosensitizer for Photodynamic Therapy: Surface Hopping and Classical Molecular Dynamics. J. Chem. Theory. Comput. 2019, 15, 5046–5057. [Google Scholar] [CrossRef]
  20. Gayathri, T.; Vijayalakshmi, A.; Mangalath, S.; Joseph, J.; Rao, N.M.; Singh, S.P. Study on Liposomal Encapsulation of New Bodipy Sensitizers for Photodynamic Therapy. ACS. Med. Chem. Lett. 2018, 9, 323–327. [Google Scholar] [CrossRef]
  21. Dai, X.M.; Chen, X.L.; Zhao, Y.; Yu, Y.J.; Wei, X.S.; Zhang, X.G.; Li, C.X. A Water-Soluble Galactose-Decorated Cationic Photodynamic Therapy Agent Based on BODIPY to Selectively Eliminate Biofilm. Biomacromolecules 2018, 19, 141–149. [Google Scholar] [CrossRef]
  22. Huang, L.; Li, Z.J.; Zhao, Y.; Zhang, Y.W.; Wu, S.; Zhao, J.Z.; Han, G. Ultralow-Power Near Infrared Lamp Light Operable Targeted Organic Nanoparticle Photodynamic Therapy. J. Am. Chem. Soc. 2016, 138, 14586–14591. [Google Scholar] [CrossRef] [PubMed]
  23. Wu, S.; Li, Y.; Deng, T.; Wang, X.; Hu, S.; Peng, G.; Huang, X.A.; Ling, Y.; Liu, F. A new fluorescent probe for sensing of biothiols and screening of acetylcholinesterase inhibitors. Org. Biomol. Chem. 2020, 18, 2468–2474. [Google Scholar] [CrossRef]
  24. Zhang, J.; Wang, N.; Ji, X.; Tao, Y.; Wang, J.; Zhao, W. BODIPY-Based Fluorescent Probes for Biothiols. Chem. Eur. J. 2020, 26, 4172–4192. [Google Scholar] [CrossRef] [PubMed]
  25. Guria, S.; Ghosh, A.; Manna, K.; Pal, A.; Adhikary, A.; Adhikari, S. Rapid detection of aspartic acid and glutamic acid in water by BODIPY-Based fluorescent probe: Live-cell imaging and DFT studies. Dyes Pigm. 2019, 168, 111–122. [Google Scholar] [CrossRef]
  26. Wijesooriya, C.S.; Peterson, J.A.; Shrestha, P.; Gehrmann, E.J.; Winter, A.H.; Smith, E.A. A Photoactivatable BODIPY Probe for Localization-Based Super-Resolution Cellular Imaging. Angew. Chem. Int. Ed. Engl. 2018, 57, 12685–12689. [Google Scholar] [CrossRef] [PubMed] [Green Version]
  27. Brommel, K.; Maskri, S.; Maisuls, I.; Konken, C.P.; Rieke, M.; Petho, Z.; Strassert, C.A.; Koch, O.; Schwab, A.; Wunsch, B. Synthesis of Small-Molecule Fluorescent Probes for the In Vitro Imaging of Calcium-Activated Potassium Channel KCa3.1. Angew. Chem. Int. Ed. Engl. 2020, 59, 2–10. [Google Scholar] [CrossRef] [Green Version]
  28. Taniguchi, A.; Sawazaki, T.; Shimizu, Y.; Sohma, Y.; Kanai, M. Photophysical properties and application in live cell imaging of B,B-fluoro-perfluoroalkyl BODIPYs. Med. Chem. Commun. 2019, 10, 1121–1125. [Google Scholar] [CrossRef]
  29. Zhang, P.-L.; Wang, Z.-K.; Chen, Q.-Y.; Du, X.; Gao, J. Biocompatible G-Quadruplex/BODIPY assembly for cancer cell imaging and the attenuation of mitochondria. Bioorg. Med. Chem. Lett. 2019, 29, 1943–1947. [Google Scholar] [CrossRef]
  30. Liu, Q.D.; Mudadu, M.S.; Thummel, R.; Tao, Y.; Wang, S. From Blue to Red: Syntheses, Structures, Electronic and Electroluminescent Properties of Tunable Luminescent N,N Chelate Boron Complexes. Adv. Funct. Mater. 2005, 15, 143–154. [Google Scholar] [CrossRef]
  31. Yang, T.; Cao, X.; Zhang, X.X.; Ou, Y.; Au, C.T.; Yin, S.F.; Qiu, R. Iodine-Catalyzed Synthesis of N,N′-Chelate Organoboron Aminoquinolate. J. Org. Chem. 2020, 85, 12430–12443. [Google Scholar] [CrossRef]
  32. Mas-Montoya, M.; Usea, L.; Espinosa Ferao, A.; Montenegro, M.F.; Ramirez de Arellano, C.; Tarraga, A.; Rodriguez-Lopez, J.N.; Curiel, D. Single Heteroatom Fine-Tuning of the Emissive Properties in Organoboron Complexes with 7-(Azaheteroaryl)indole Systems. J. Org. Chem. 2016, 81, 3296–3302. [Google Scholar] [CrossRef] [PubMed]
  33. Shiu, Y.J.; Cheng, Y.C.; Tsai, W.L.; Wu, C.C.; Chao, C.T.; Lu, C.W.; Chi, Y.; Chen, Y.T.; Liu, S.H.; Chou, P.T. Pyridyl Pyrrolide Boron Complexes: The Facile Generation of Thermally Activated Delayed Fluorescence and Preparation of Organic Light-Emitting Diodes. Angew. Chem. Int. Ed. Engl. 2016, 55, 3017–3021. [Google Scholar] [CrossRef] [PubMed]
  34. Nagata, Y.; Chujo, Y. Main-Chain-Type N,N′-Chelate Organoboron Aminoquinolate Polymers: Synthesis, Luminescence, and Energy Transfer Behavior. Macromolecules 2008, 41, 3488–3492. [Google Scholar] [CrossRef]
  35. Zu, W.; Day, C.; Wei, L.; Jia, X.; Xu, L. Dual aminoquinolate diarylboron and nickel catalysed metallaphotoredox platform for carbon-oxygen bond construction. Chem. Commun. 2020, 56, 8273–8276. [Google Scholar] [CrossRef] [PubMed]
  36. Liu, S.-F.; Wu, Q.; Schmider, H.L.; Aziz, H.; Hu, N.-X.; Popovic, Z.; Wang, S. Syntheses, Structures, and Electroluminescence of New Blue/Green Luminescent Chelate Compounds: Zn(2-py-in)2(THF), BPh2(2-py-in), Be(2-py-in)2, and BPh2(2-py-aza) [2-py-in ) 2-(2-pyridyl)indole; 2-py-aza ) 2-(2-pyridyl)-7-azaindole]. J. Am. Chem. Soc. 2000, 122, 3671–3678. [Google Scholar] [CrossRef]
  37. Narula, C.K.; Noeth, H. Competition between adduct and cation formation in reactions between diorganylborane derivatives and pyridine or lutidines. Inorg. Chem. 1985, 24, 2532–2539. [Google Scholar] [CrossRef]
  38. Ding, L.; Ma, K.; Dürner, G.; Bolte, M.; Fabrizi de Biani, F.; Zanello, P.; Wagner, M. Reactions of ferrocenylboranes with 2,5-bis(pyridyl)pyrazine and quaterpyridine: Charge-transfer complexes and redox-active macrocycles. J. Chem. Soc., Dalton Trans. 2002, 8, 1566–1573. [Google Scholar] [CrossRef]
  39. Ding, L.; Ma, K.; Fabrizi de Biani, F.; Bolte, M.; Zanello, P.; Wagner, M. Electronic Communication in a Novel Five-Step Redox System. Organometallics 2001, 20, 1041–1043. [Google Scholar] [CrossRef]
  40. Ma, K.; Fabrizi de Biani, F.; Bolte, M.; Zanello, P.; Wagner, M. Electronic Communication in a Series of Novel Multistep Redox Systems. Organometallics 2002, 21, 3979–3989. [Google Scholar] [CrossRef]
  41. Haberecht, M.C.; Bolte, M.; Lerner, H.-W.; Wagner, M. An Approach towards Functional Dendrimers Based on the Hydroboration Reaction and Spontaneous Boron-Nitrogen Bond Formation. Eur. J. Inorg. Chem. 2005, 2005, 4309–4316. [Google Scholar] [CrossRef]
  42. Wood, T.K.; Piers, W.E.; Keay, B.A.; Parvez, M. Spirocyclic boronium ions: Precursors to persistent neutral radicals. Chem. Commun. 2009, 34, 5147–5149. [Google Scholar] [CrossRef] [PubMed] [Green Version]
  43. Cui, C.; Heilmann-Brohl, J.; Sánchez Perucha, A.; Thomson, M.D.; Roskos, H.G.; Wagner, M.; Jäkle, F. Redox-Active Ferrocenylboronium Polyelectrolytes with Main Chain Charge-Transfer Structure. Macromolecules 2010, 43, 5256–5261. [Google Scholar] [CrossRef]
  44. Januszewski, E.; Lorbach, A.; Grewal, R.; Bolte, M.; Bats, J.W.; Lerner, H.W.; Wagner, M. Unsymmetrically substituted 9,10-dihydro-9,10-diboraanthracenes as versatile building blocks for boron-doped pi-conjugated systems. Chem. Eur. J. 2011, 17, 12696–12705. [Google Scholar] [CrossRef]
  45. Liu, Q.; Mudadu, M.S.; Schmider, H.; Thummel, R.; Tao, Y.; Wang, S. Tuning the Luminescence and Electroluminescence of Diphenylboron Complexes of 5-Substituted 2-(2′-Pyridyl)indoles. Organometallics 2002, 21, 4743–4749. [Google Scholar] [CrossRef]
  46. Scheibitz, M.; Heilmann, J.B.; Winter, R.F.; Bolte, M.; Bats, J.W.; Wagner, M. Electronic interactions in oligoferrocenes with cationic, neutral and anionic four-coordinate boron bridges. Dalton Trans. 2005, 1, 159–170. [Google Scholar] [CrossRef] [PubMed] [Green Version]
  47. Cheng, C.C.; Yu, W.S.; Chou, P.T.; Peng, S.M.; Lee, G.H.; Wu, P.C.; Song, Y.H.; Chi, Y. Syntheses and remarkable photophysical properties of 5-(2-pyridyl) pyrazolate boron complexes; photoinduced electron transfer. Chem. Commun. 2003, 20, 2628–2629. [Google Scholar] [CrossRef] [PubMed] [Green Version]
  48. Andrade-López, N.; Alvarado-Rodríguez, J.G.; Flores-Chávez, B. Synthesis and crystal structure of the N-8-(diphenyl-hydroxy-2-aminomethylpyridine)borane. J. Chem. Crystallogr. 2005, 35, 191–196. [Google Scholar] [CrossRef]
  49. Ho, M.L.; Hwang, F.M.; Chen, P.N.; Hu, Y.H.; Cheng, Y.M.; Chen, K.S.; Lee, G.H.; Chi, Y.; Chou, P.T. Design and synthesis of iridium(III) azacrown complex: Application as a highly sensitive metal cation phosphorescence sensor. Org. Biomol. Chem. 2006, 4, 98–103. [Google Scholar] [CrossRef] [PubMed] [Green Version]
  50. Dijkstra, P.; Angelone, D.; Talnishnikh, E.; Wortche, H.J.; Otten, E.; Browne, W.R. Pyridyl-1,2,4-triazole diphenyl boron complexes as efficient tuneable blue emitters. Dalton Trans. 2014, 43, 17740–17745. [Google Scholar] [CrossRef]
  51. Sadu, V.S.; Bin, H.R.; Lee, D.M.; Lee, K.I. One-pot synthesis of four-coordinate boron(III) complexes by the ligand-promoted organic group migration between boronic acids. Sci. Rep. 2017, 7, 242. [Google Scholar] [CrossRef] [PubMed] [Green Version]
  52. Chen, H.Y.; Chi, Y.; Liu, C.S.; Yu, J.K.; Cheng, Y.M.; Chen, K.S.; Chou, P.T.; Peng, S.M.; Lee, G.H.; Carty, A.J.; et al. Rational Color Tuning and Luminescent Properties of Functionalized Boron-Containing 2-Pyridyl Pyrrolide Complexes. Adv. Funct. Mater. 2005, 15, 567–574. [Google Scholar] [CrossRef]
  53. Chen, T.-R.; Chien, R.-H.; Yeh, A.; Chen, J.-D. Synthesis, characterization and electroluminescence of B(III) compounds: BPh2(2-(2-quinolyl)naphtho[b]imidazolato) and BPh2(2-(2-quinolyl)benzimidazolato). J. Organomet. Chem. 2006, 691, 1998–2004. [Google Scholar] [CrossRef]
  54. Chen, D.-G.; Ranganathan, R.; Lin, J.-A.; Huang, C.-Y.; Ho, M.-L.; Chi, Y.; Chou, P.-T. Ratiometric Tuning of Luminescence: Interplay between the Locally Excited and Interligand Charge-Transfer States in Pyrazolate-Based Boron Compounds. J. Phys. Chem. C 2019, 123, 4022–4028. [Google Scholar] [CrossRef]
  55. Tokoro, Y.; Nagai, A.; Chujo, Y. Luminescent chiral organoboron 8-aminoquinolate-coordination polymers. Appl. Organomet. Chem. 2009, 24, 563–568. [Google Scholar] [CrossRef]
  56. Tokoro, Y.; Nagai, A.; Chujo, Y. Synthesis of highly luminescent organoboron polymers connected by bifunctional 8-aminoquinolate linkers. J. Polym. Sci., Part A: Polym. Chem. 2010, 48, 3693–3701. [Google Scholar] [CrossRef]
  57. Tokoro, Y.; Nagai, A.; Tanaka, K.; Chujo, Y. Synthesis of π-conjugated polymers containing aminoquinoline-borafluorene complexes in the main-chain. Macromol. Rapid Commun. 2012, 33, 550–555. [Google Scholar] [CrossRef]
  58. Caputo, C.B.; Geier, S.J.; Winkelhaus, D.; Mitzel, N.W.; Vukotic, V.N.; Loeb, S.J.; Stephan, D.W. Reactions of substituted pyridines with electrophilic boranes. Dalton Trans. 2012, 41, 2131–2139. [Google Scholar] [CrossRef] [PubMed]
  59. Mahdi, T.; del Castillo, J.N.; Stephan, D.W. Metal-Free Hydrogenation of N-Based Heterocycles. Organometallics 2013, 32, 1971–1978. [Google Scholar] [CrossRef]
  60. Yoshino, J.; Sekikawa, T.; Hatta, N.; Hayashi, N.; Higuchi, H. Photoinduced solid-state coloring behavior of boronium complexes. Tetrahedron Lett. 2016, 57, 5489–5492. [Google Scholar] [CrossRef]
  61. Bamford, K.L.; Longobardi, L.E.; Liu, L.; Grimme, S.; Stephan, D.W. FLP reduction and hydroboration of phenanthrene o-iminoquinones and α-diimines. Dalton Trans. 2017, 46, 5308–5319. [Google Scholar] [CrossRef] [PubMed]
  62. Yamagata, T.; Kuwabara, J.; Kanbara, T. Optical properties of highly planar diketopyrrolopyrrole derivatives fixed by coordinate bonds. Tetrahedron 2014, 70, 1451–1457. [Google Scholar] [CrossRef] [Green Version]
  63. Kanbara, T.; Yamagata, T.; Kuwabara, J. Synthesis and Photophysical Properties of Diketopyrrolopyrrole-Based Near-Infrared Dyes. Heterocycles 2014, 89, 1173. [Google Scholar] [CrossRef]
  64. Huang, K.; Martin, C.D. Peculiar Reactivity of Isothiocyanates with Pentaphenylborole. Inorg. Chem. 2016, 55, 330–337. [Google Scholar] [CrossRef] [PubMed]
Molecules 26 01401 g001 550
Figure 1. Application of tetracoordinate organoboron complexes in luminescent materials, organic light-emitting diode (OLED), functional polymer, and photocatalyst [30,31,32,33,34,35,36].
Figure 1. Application of tetracoordinate organoboron complexes in luminescent materials, organic light-emitting diode (OLED), functional polymer, and photocatalyst [30,31,32,33,34,35,36].
Molecules 26 01401 g001
Molecules 26 01401 g002 550
Figure 2. The methods for the formation of N,N′-chelate organoboron derivatives [30,31,32,33,34,35,36].
Figure 2. The methods for the formation of N,N′-chelate organoboron derivatives [30,31,32,33,34,35,36].
Molecules 26 01401 g002
Molecules 26 01401 sch001 550
Scheme 1. Reactions of bipyridine with dibutyl(((trifluoromethyl)sulfonyl)oxy)borane [37].
Scheme 1. Reactions of bipyridine with dibutyl(((trifluoromethyl)sulfonyl)oxy)borane [37].
Molecules 26 01401 sch001
Molecules 26 01401 sch002 550
Scheme 2. Reactions of 2,5-di(pyridin-2-yl)pyrazine (or 2′, 2′: 4′, 4′: 2″, 2‴-quaterpyridine) with FcB(Me)Br [38].
Scheme 2. Reactions of 2,5-di(pyridin-2-yl)pyrazine (or 2′, 2′: 4′, 4′: 2″, 2‴-quaterpyridine) with FcB(Me)Br [38].
Molecules 26 01401 sch002
Molecules 26 01401 sch003 550
Scheme 3. The methods for the synthesis of {Fc(Bbipy)2O}(PF6)2 and {Fc(Bbipy)2(OH)2}(PF6)2 [39,40].
Scheme 3. The methods for the synthesis of {Fc(Bbipy)2O}(PF6)2 and {Fc(Bbipy)2(OH)2}(PF6)2 [39,40].
Molecules 26 01401 sch003
Molecules 26 01401 sch004 550
Scheme 4. Reactions of 4,4′-di(but-3-en-1-yl)-2,2′-bipyridine with trivalent boron [41].
Scheme 4. Reactions of 4,4′-di(but-3-en-1-yl)-2,2′-bipyridine with trivalent boron [41].
Molecules 26 01401 sch004
Molecules 26 01401 sch005 550
Scheme 5. Reactions of bipyridine with 5-chloro-5,10-dihydrodibenzo[b,e]borinine [42].
Scheme 5. Reactions of bipyridine with 5-chloro-5,10-dihydrodibenzo[b,e]borinine [42].
Molecules 26 01401 sch005
Molecules 26 01401 sch006 550
Scheme 6. Bipyridine for the formation of N,N′-chelate organoboron and ferrocene derivatives [43].
Scheme 6. Bipyridine for the formation of N,N′-chelate organoboron and ferrocene derivatives [43].
Molecules 26 01401 sch006
Molecules 26 01401 sch007 550
Scheme 7. Bipyridine reacting with 5-bromo-10-mesityl-5,10-dihydroboranthrene [44].
Scheme 7. Bipyridine reacting with 5-bromo-10-mesityl-5,10-dihydroboranthrene [44].
Molecules 26 01401 sch007
Molecules 26 01401 sch008 550
Scheme 8. Reactions of 2-(pyridin-2-yl)-1H-indole and 2-(pyridin-2-yl)-1H-pyrrolo[2,3-b]pyridine with BPh3 [36].
Scheme 8. Reactions of 2-(pyridin-2-yl)-1H-indole and 2-(pyridin-2-yl)-1H-pyrrolo[2,3-b]pyridine with BPh3 [36].
Molecules 26 01401 sch008
Molecules 26 01401 sch009 550
Scheme 9. Reactions of 2-(pyridin-2-yl)-1H-indole derivatives with BPh3 [45].
Scheme 9. Reactions of 2-(pyridin-2-yl)-1H-indole derivatives with BPh3 [45].
Molecules 26 01401 sch009
Molecules 26 01401 sch010 550
Scheme 10. Reactions of 2-(1H-indol-2-yl)thiazole, 8-(1H-benzo[d]imidazol-2-yl)quinoline, and their analogues with BPh3 [30].
Scheme 10. Reactions of 2-(1H-indol-2-yl)thiazole, 8-(1H-benzo[d]imidazol-2-yl)quinoline, and their analogues with BPh3 [30].
Molecules 26 01401 sch010
Molecules 26 01401 sch011 550
Scheme 11. Reactions of 2-(pyridin-2-yl)-1H-indole with FcBMeBr [46].
Scheme 11. Reactions of 2-(pyridin-2-yl)-1H-indole with FcBMeBr [46].
Molecules 26 01401 sch011
Molecules 26 01401 sch012 550
Scheme 12. Reactions of 2-(1H-indol-7-yl)benzo[d]oxazole, 2-(1H-indol-7-yl)benzo[d]thiazole, and 2-(1H-indol-7-yl)-1-octyl-1H-benzo[d]imidazole with BPh3 [32].
Scheme 12. Reactions of 2-(1H-indol-7-yl)benzo[d]oxazole, 2-(1H-indol-7-yl)benzo[d]thiazole, and 2-(1H-indol-7-yl)-1-octyl-1H-benzo[d]imidazole with BPh3 [32].
Molecules 26 01401 sch012
Molecules 26 01401 sch013 550
Scheme 13. Reactions of 2-(1H-pyrazol-5-yl)pyridine reacting with BPh3 [47].
Scheme 13. Reactions of 2-(1H-pyrazol-5-yl)pyridine reacting with BPh3 [47].
Molecules 26 01401 sch013
Molecules 26 01401 sch014 550
Scheme 14. Reactions of pyridin-2-ylmethanamine with hydroxydiphenylborane [48].
Scheme 14. Reactions of pyridin-2-ylmethanamine with hydroxydiphenylborane [48].
Molecules 26 01401 sch014
Molecules 26 01401 sch015 550
Scheme 15. Reactions of 2-(1H-pyrazol-5-yl)pyridine derivatives with BPh3 [49].
Scheme 15. Reactions of 2-(1H-pyrazol-5-yl)pyridine derivatives with BPh3 [49].
Molecules 26 01401 sch015
Molecules 26 01401 sch016 550
Scheme 16. Reactions of 2-(4H-1,2,4-triazol-3-yl)pyridine derivatives with BPh3 [50].
Scheme 16. Reactions of 2-(4H-1,2,4-triazol-3-yl)pyridine derivatives with BPh3 [50].
Molecules 26 01401 sch016
Molecules 26 01401 sch017 550
Scheme 17. Synthesis of 2-(3,5-bis(trifluoromethyl)-1H-pyrrol-2-yl)pyridine chelate organoboron complexes [33].
Scheme 17. Synthesis of 2-(3,5-bis(trifluoromethyl)-1H-pyrrol-2-yl)pyridine chelate organoboron complexes [33].
Molecules 26 01401 sch017
Molecules 26 01401 sch018 550
Scheme 18. Reactions of 2-(5-methyl-1H-pyrrol-2-yl)pyridine, 2-(pyridin-2-yl)-1H-indole, and (Z)-2-(phenyl(2H-pyrrol-2-ylidene)methyl)-1H-pyrrole with BPh3 [51].
Scheme 18. Reactions of 2-(5-methyl-1H-pyrrol-2-yl)pyridine, 2-(pyridin-2-yl)-1H-indole, and (Z)-2-(phenyl(2H-pyrrol-2-ylidene)methyl)-1H-pyrrole with BPh3 [51].
Molecules 26 01401 sch018
Molecules 26 01401 sch019 550
Scheme 19. Reactions of 2-(5-methyl-1H-pyrrol-2-yl)pyridine, 2-(5-methyl-1H-pyrrol-2-yl)quinoline, and 2-(5-methyl-1H-pyrrol-2-yl)quinoxaline with BPh3 [52].
Scheme 19. Reactions of 2-(5-methyl-1H-pyrrol-2-yl)pyridine, 2-(5-methyl-1H-pyrrol-2-yl)quinoline, and 2-(5-methyl-1H-pyrrol-2-yl)quinoxaline with BPh3 [52].
Molecules 26 01401 sch019
Molecules 26 01401 sch020 550
Scheme 20. Synthesis of BPh2(2-(2-quinolyl)naphtho[b]imidazolato) and BPh2(2-(2-quinolyl)benzimidazolato) [53].
Scheme 20. Synthesis of BPh2(2-(2-quinolyl)naphtho[b]imidazolato) and BPh2(2-(2-quinolyl)benzimidazolato) [53].
Molecules 26 01401 sch020
Molecules 26 01401 sch021 550
Scheme 21. Synthesis of 1-(3-(trifluoromethyl)-1H-pyrazol-5-yl)isoquinoline chelate organoboron complexes [54].
Scheme 21. Synthesis of 1-(3-(trifluoromethyl)-1H-pyrazol-5-yl)isoquinoline chelate organoboron complexes [54].
Molecules 26 01401 sch021
Molecules 26 01401 sch022 550
Scheme 22. Reactions of N-(quinolin-8-yl)acetamide with BPh3 [34].
Scheme 22. Reactions of N-(quinolin-8-yl)acetamide with BPh3 [34].
Molecules 26 01401 sch022
Molecules 26 01401 sch023 550
Scheme 23. Synthesis of (S)-N-(1-((5-iodoquinolin-8-yl)amino)-1-oxopropan-2-yl)hexanamide chelate organoboron polymer [55].
Scheme 23. Synthesis of (S)-N-(1-((5-iodoquinolin-8-yl)amino)-1-oxopropan-2-yl)hexanamide chelate organoboron polymer [55].
Molecules 26 01401 sch023
Molecules 26 01401 sch024 550
Scheme 24. Synthesis of N-(5-iodoquinolin-8-yl)undecanamide chelate organoboron polymer [56].
Scheme 24. Synthesis of N-(5-iodoquinolin-8-yl)undecanamide chelate organoboron polymer [56].
Molecules 26 01401 sch024
Molecules 26 01401 sch025 550
Scheme 25. Synthesis of N-(quinolin-8-yl)acetamide chelate organoboron polymer [57].
Scheme 25. Synthesis of N-(quinolin-8-yl)acetamide chelate organoboron polymer [57].
Molecules 26 01401 sch025
Molecules 26 01401 sch026 550
Scheme 26. Synthesis of quinolin-8-amine chelate organoboron complex [58].
Scheme 26. Synthesis of quinolin-8-amine chelate organoboron complex [58].
Molecules 26 01401 sch026
Molecules 26 01401 sch027 550
Scheme 27. Synthesis of 3-phenyl-N-(quinolin-8-yl)propanamide derivatives chelate organoboron photocatalysts [35].
Scheme 27. Synthesis of 3-phenyl-N-(quinolin-8-yl)propanamide derivatives chelate organoboron photocatalysts [35].
Molecules 26 01401 sch027
Molecules 26 01401 sch028 550
Scheme 28. Synthesis of 2,2,2-trifluoro-N-(quinolin-8-yl)acetamide-based organoboron fluorescent complexes [31].
Scheme 28. Synthesis of 2,2,2-trifluoro-N-(quinolin-8-yl)acetamide-based organoboron fluorescent complexes [31].
Molecules 26 01401 sch028
Molecules 26 01401 sch029 550
Scheme 29. Synthesis of 1,10-phenanthroline chelate organoboron complex [59].
Scheme 29. Synthesis of 1,10-phenanthroline chelate organoboron complex [59].
Molecules 26 01401 sch029
Molecules 26 01401 sch030 550
Scheme 30. Synthesis of 1,10-phenanthroline chelate organoboron complex [60].
Scheme 30. Synthesis of 1,10-phenanthroline chelate organoboron complex [60].
Molecules 26 01401 sch030
Molecules 26 01401 sch031 550
Scheme 31. Reactions of (9E,10E)-N9,N10-bis(6-methylheptyl)phenanthrene-9,10-diimine with trivalent boron [61].
Scheme 31. Reactions of (9E,10E)-N9,N10-bis(6-methylheptyl)phenanthrene-9,10-diimine with trivalent boron [61].
Molecules 26 01401 sch031
Molecules 26 01401 sch032 550
Scheme 32. Synthesis of boron-coordinated diketopyrrolopyrrole (DPP) derivatives [62].
Scheme 32. Synthesis of boron-coordinated diketopyrrolopyrrole (DPP) derivatives [62].
Molecules 26 01401 sch032
Molecules 26 01401 sch033 550
Scheme 33. Synthesis of boron-coordinated diketopyrrolopyrrole (DPP) derivatives [63].
Scheme 33. Synthesis of boron-coordinated diketopyrrolopyrrole (DPP) derivatives [63].
Molecules 26 01401 sch033
Molecules 26 01401 sch034 550
Scheme 34. Reactions of 1,2,3,4,5-pentaphenyl-1H-borole with isocyanates [64].
Scheme 34. Reactions of 1,2,3,4,5-pentaphenyl-1H-borole with isocyanates [64].
Molecules 26 01401 sch034
Publisher’s Note: MDPI stays neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Share and Cite

MDPI and ACS Style

Yang, T.; Tang, N.; Wan, Q.; Yin, S.-F.; Qiu, R. Recent Progress on Synthesis of N,N′-Chelate Organoboron Derivatives. Molecules 2021, 26, 1401. https://doi.org/10.3390/molecules26051401

AMA Style

Yang T, Tang N, Wan Q, Yin S-F, Qiu R. Recent Progress on Synthesis of N,N′-Chelate Organoboron Derivatives. Molecules. 2021; 26(5):1401. https://doi.org/10.3390/molecules26051401

Chicago/Turabian Style

Yang, Tianbao, Niu Tang, Qizhong Wan, Shuang-Feng Yin, and Renhua Qiu. 2021. "Recent Progress on Synthesis of N,N′-Chelate Organoboron Derivatives" Molecules 26, no. 5: 1401. https://doi.org/10.3390/molecules26051401

APA Style

Yang, T., Tang, N., Wan, Q., Yin, S. -F., & Qiu, R. (2021). Recent Progress on Synthesis of N,N′-Chelate Organoboron Derivatives. Molecules, 26(5), 1401. https://doi.org/10.3390/molecules26051401

Article Metrics

Back to TopTop