Synthesis and properties of fluorescent organoboranes: triarylmethane-type dyes

Albrecht, K.; Kaiser, V.; Boese, Roland; Adams, Jörg; Kaufmann, Dieter

doi:10.1039/b002184i

Cited by 29 publications

(24 citation statements)

References 27 publications

(4 reference statements)

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“…Crystallographic data and refinement parameters are given in Table 1. The crystal structures of the related molecules phenyldimesitylborane 1-H [14] at 188 K, [2-(N,N-dimethylamino)phenyl]dimesitylborane, [15] and (mesitylethynyl)dimesi-tylborane at room temperature [16] have been reported previously. All of the compounds crystallize with one molecule in the asymmetric unit, apart from 4 which has two independent molecules.…”

Section: Resultsmentioning

confidence: 97%

Synthesis, Crystal Structures, Linear and Nonlinear Optical Properties, and Theoretical Studies of (p‐R‐Phenyl)‐, (p‐R‐Phenylethynyl)‐, and (E)‐[2‐(p‐R‐Phenyl)ethenyl]dimesitylboranes and Related Compounds

Zheng

Entwistle

Collings

et al. 2006

Chemistry A European J

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221

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The (p-R-phenyl)dimesitylboranes (R=Me(2)N, MeO, MeS, Br, I), (p-R-phenylethynyl)dimesitylboranes (R=Me(2)N, MeO, MeS, H), (E)-[2-(p-R-phenyl)ethenyl]dimesitylboranes (R=Me(2)N, H(2)N, MeO, MeS, H, CN, NO(2)), (E)-[2-(2-thienyl)ethenyl]dimesitylborane, and (E)-[2-(o-carboranyl)ethenyl]dimesitylborane have been prepared through the reaction of the appropriate p-R-phenyl- and p-R-phenylethynyllithium reagents with dimesitylboron fluoride and by hydroboration of the appropriate p-R-phenylacetylene, 2-ethynylthiophene, and o-ethynylcarborane with dimesitylborane. Their UV/Vis absorption and emission spectra have been recorded in a range of solvents with the fluorescence maxima of the donor-substituted compounds in particular exhibiting large bathochromic shifts in highly polar solvents, indicative of charge transfer leading to large dipole moments in the excited state. The molecular structures of the (p-R-phenyl)dimesitylboranes (R=Me(2)N, MeO, MeS, Br, I), the (E)-[2-(p-R-phenyl)ethenyl]dimesitylboranes (R=Me(2)N, H(2)N MeO, MeS, H), (p-R-phenylethynyl)dimesitylborane (R=Me(2)N), and (E)-[2-(2-thienyl)ethenyl]dimesitylborane, which have been determined from single-crystal X-ray diffraction measurements, offer evidence of increased conjugation in the ground state with increased donor strength of the R substituent. Their first- and second-order molecular hyperpolarizabilities have been obtained from EFISH and THG measurements, the first-order hyperpolarizabilities being largest for the strongest R-substituent donors. AM1 calculations have been performed on these compounds, showing reasonable agreement with the experimentally obtained bond lengths and hyperpolarizabilities, as well as on several related hypothetical compounds containing multiple C==C bonds, most of which are proposed to have even larger hyperpolarizabilities.

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Section: Resultsmentioning

confidence: 97%

Synthesis, Crystal Structures, Linear and Nonlinear Optical Properties, and Theoretical Studies of (p‐R‐Phenyl)‐, (p‐R‐Phenylethynyl)‐, and (E)‐[2‐(p‐R‐Phenyl)ethenyl]dimesitylboranes and Related Compounds

Zheng

Entwistle

Collings

et al. 2006

Chemistry A European J

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221

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“…Aus späteren Untersuchungen ergab sich jedoch, dass B(Mes) 2 in seiner elektronenziehenden Kraft tatsächlich der Cyangruppe nahe kommt 25. Kürzlich wurde auch die Photophysik einiger verwandter ortho ‐substituierter PhB(Mes) 2 ‐Derivate untersucht 30…”

Section: Dreifach Koordiniertes Borunclassified

Die Borchemie leuchtet: optische Eigenschaften von MolekÃ¼len und Polymeren C.D.E. dankt EPSRC und Syngenta fÃ¼r Postgraduiertenstipendien und T.B.M. der University of Durham fÃ¼r UnterstÃ¼tzung sowie Prof. Dr. K. Tamao fÃ¼r einen Vorabdruck von Lit. 32.

2002

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Elektrooptische und elektronische Materialien sind Gegenstand großer Forschungsaktivität; dabei konzentrierte man sich bisher auf elektronenreiche organische Moleküle. In den letzten Jahren wurden neue Wege zu Elektronenmangelsystemen entwickelt, wobei man sich zunutze machte, dass dreifach koordiniertes Bor und das positiv geladene Carbokation isoelektronisch und gleichartig von ihren Substituenten umgeben sind, was die direkte Synthese von neutralen p‐Typ‐Materialien ermöglichte. Dieser Kurzaufsatz fasst neuere Arbeiten über Verbindungen mit drei‐ und vierfach koordiniertem Bor und über Borcluster zusammen und verknüpft sie mit früheren Untersuchungen der Arbeitsgruppen von Williams und Glowgowski, Kaim, Lequan und Marder.

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“…These results suggest that aminoboranes are the best suited for the catalytic hydrogenation of CO2 [71]. Whereas many intramolecular aminoboranes have been reported and that some of them have been used to catalyze hydrogenation reactions [72][73][74][75][76][77][78][79][80], none were reported to effect the hydrogenation of carbon dioxide. It should be noted that an important side reaction in the activation of H2 using 1-NR2-2-B(C6F5)2-C6H4 is the protodeborylation reaction where the acidic proton on nitrogen once H2 is cleaved is transferred to one of the pentafluoroaryl groups to generate C6F5H (Scheme 13).…”

Section: Developing a System For The Metal-free Hydrogenation Of Co2mentioning

confidence: 99%

Design principles in frustrated Lewis pair catalysis for the functionalization of carbon dioxide and heterocycles

Fontaine

Courtemanche

Légaré

et al. 2017

Coordination Chemistry Reviews

102

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This is the peer reviewed version of the following article: [Design Principles in Frustrated Lewis KeywordsFrustrated Lewis pairs, Ambiphilic molecules, Boron, Aluminum, Carbon dioxide, Methanol, C-H activation. Highlights 1.Phosphine-aluminum frustrated Lewis pairs (FLPs) can activate CO2 but show significant stability issues. 2.The Lewis acidity and basicity need to be fine-tuned to the desired reactivity for efficient FLP catalysis.3. FLP catalysts need to generate strong hydrides to reduce catalytically carbon dioxide. 4.Transition metal catalysis can serve as an inspiration for the design of metal-free catalysts for many transformations, including the borylation of heteroarenes. Graphical abstract AbstractThis account describes our work on the use of ambiphilic molecules as catalysts for the reduction of carbon dioxide. Starting with the discovery that aluminum ambiphilic species (Me2PCH2AlMe2)2 (1) and Al(C6H4-PPh3)3 (5) could coordinate CO2 but showed significant instability, we found that phosphinoborane Ph2P-2-Bcat-C6H4 (7) was an exceptional catalyst for the hydroboration of CO2 to methoxyboranes, a molecule that can be readily hydrolyzed to methanol. A mechanistic investigation allowed us to outline the similarities between the catalytic activity of frustrated Lewis pairs (FLPs) and that of transition metal complexes. We were able to extrapolate four important guidelines, described in this account, to synthesize efficient metal-free catalysts. We demonstrate that using these concepts it was possible to rationally design FLP catalysts for the C-H borylation of heteroarenes.

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Synthesis and properties of fluorescent organoboranes: triarylmethane-type dyes

Cited by 29 publications

References 27 publications

Synthesis, Crystal Structures, Linear and Nonlinear Optical Properties, and Theoretical Studies of (p‐R‐Phenyl)‐, (p‐R‐Phenylethynyl)‐, and (E)‐[2‐(p‐R‐Phenyl)ethenyl]dimesitylboranes and Related Compounds

Synthesis, Crystal Structures, Linear and Nonlinear Optical Properties, and Theoretical Studies of (p‐R‐Phenyl)‐, (p‐R‐Phenylethynyl)‐, and (E)‐[2‐(p‐R‐Phenyl)ethenyl]dimesitylboranes and Related Compounds

Die Borchemie leuchtet: optische Eigenschaften von MolekÃ¼len und Polymeren C.D.E. dankt EPSRC und Syngenta fÃ¼r Postgraduiertenstipendien und T.B.M. der University of Durham fÃ¼r UnterstÃ¼tzung sowie Prof. Dr. K. Tamao fÃ¼r einen Vorabdruck von Lit. 32.

Design principles in frustrated Lewis pair catalysis for the functionalization of carbon dioxide and heterocycles

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