On the ambiguity of 1,3,2-benzodiazaboroles as donor/acceptor functionalities in luminescent molecules

Abstract

Citation for published item:eerD vF nd rlmD tF nd rnkeD uF nd f¤ ohlingD vF nd frokhinkeD eF nd tmmlerD rFEqF nd xeumnnD fF nd poxD wFeF @PHIRA 9yn the miguity of IDQDPEenzodizoroles s donorGeptor funtionlities in luminesent moleulesF9D hlton trnstionsFD RQ @VAF ppF QQRUEQQTQF Further information on publisher's website: Use policyThe full-text may be used and/or reproduced, and given to third parties in any format or medium, without prior permission or charge, for personal research or study, educational, or not-for-prot purposes provided that:• a full bibliographic reference is made to the original source • a link is made to the metadata record in DRO • the full-text is not changed in any way The full-text must not be sold in any format or medium without the formal permission of the copyright holders.Please consult the full DRO policy for further details. Accepted ManuscriptThis is an Accepted Manuscript, which has been through the RSC Publishing peer review process and has been accepted for publication.Accepted Manuscripts are published online shortly after acceptance, which is prior to technical editing, formatting and proof reading. This free service from RSC Publishing allows authors to make their results available to the community, in citable form, before publication of the edited article. This Accepted Manuscript will be replaced by the edited and formatted Advance Article as soon as this is available.To cite this manuscript please use its permanent Digital Object Identifier (DOI®), which is identical for all formats of publication.More information about Accepted Manuscripts can be found in the Information for Authors.Please note that technical editing may introduce minor changes to the text and/or graphics contained in the manuscript submitted by the author(s) which may alter content, and that the standard Terms & Conditions and the ethical guidelines that apply to the journal are still applicable. In no event shall the RSC be held responsible for any errors or omissions in these Accepted Manuscript manuscripts or any consequences arising from the use of any information contained in them.www.rsc.org/dalton ISSN 1477-9226 Dalton TransactionsAn international journal of inorganic chemistry 1477-9226(2010) 1On the Ambiguity of 1,3,2-Benzodiazaboroles as Donor/Acceptor Functionalities in Luminescent MoleculesLothar Weber *[a] , Johannes Halama [a] , Kenny Hanke [a] , Lena Böhling [a] , Andreas Brockhinke * [a] , Hans-Georg Stammler [a] , Beate Neumann [a] and Mark A. Fox [b] Keywords: Boron / Diazaboroles / Perfluoroaryls / Photophysics Summary:A series of 1,3-bis(perfluoroaryl)-2-(hetero)aryl-1,3,2-benzodiazaboroles, 1,3- . The X-ray structures of 8, 11, 12 and 13 were determined. Electronic structure calculations reveal that the LUMOs are located at the perfluoroaryl groups in 5-14 thus the fluorinated benzodiazaborolyl groups are considered as electron-withdrawing moieties. These moieties differ from alkylated benzodiazaborolyl groups which are regarded as donors. The emission spectra ...

Hexadentate Poly‐Lewis Acids Based on 1,3,5‐Trisilacyclohexane

“…Analogous substitution experiments with haloboranes, which are clearly more Lewis acidic than chlorocatecholborane (e. g.: ClB(C 6 F 5 ) 2 , ClBPh 2 , BrBMe 2 ), using the model system Me 3 SnC≡CSiMe 3 did not lead to the desired exchange reactions, and always resulted in mixtures. Neither experiments under thermodynamic control (starting from −78 °C and slowly warming to r.t.) nor under application of the less acidic triphenylphosphane adducts [24] of the boranes allowed the isolation of the corresponding Si−C≡C−B compounds. Presumably, the increased acidity is at the expense of selectivity of the reaction.…”

Near‐Infrared Quadrupolar Chromophores Combining Three‐Coordinate Boron‐Based Superdonor and Superacceptor Units

“…[9] Several molecules bearing this substituent as the acceptor have been found to display significant red shifts in their absorption and emission maxima, as well as much lower reduction potentials and higher stability than their nonfluorinated counterparts. [11] TheB raunschweig group has been heavily involved in the development of subvalent boron compounds, namely borylenes [12] and diborenes, [13] which are formally B I species,and thus highly electron rich. Fore xample,t he 1,3,2-benzodiazaborolyl group has been used effectively by Weber,F ox, Marder and co-workers as the donor in conjugated donor-acceptor systems (see Figure 1).…”

“…Fore xample,t he 1,3,2-benzodiazaborolyl group has been used effectively by Weber,F ox, Marder and co-workers as the donor in conjugated donor-acceptor systems (see Figure 1). [11] TheB raunschweig group has been heavily involved in the development of subvalent boron compounds, namely borylenes [12] and diborenes, [13] which are formally B I species,and thus highly electron rich. Indeed, the high-energy highest occupied molecular orbitals (HOMO) of these molecules typically lead to small HOMO-LUMO gaps and visible light absorption (and sometimes emission) in the absence of explicit acceptor moieties.…”

Dreifach koordiniertes Bor als Superdonor und ‐akzeptor für quadrupolare Nahinfrarot‐Chromophore

“…[9] Viele Moleküle,die diesen Substituenten als Akzeptor tragen, zeigen signifikante Rotverschiebungen in ihren Absorptions-und Emissionsmaxima, sowie erheblich niedrigere Reduktionspotentiale und eine hçhere Stabilitäti mV ergleich zu ihren nicht-fluorierten Gegenstücken. [11] Die Gruppe um Braunschweig beschäftigt sich seit einigen Jahren mit der Entwicklung niedervalenter Borverbindungen, nämlich mit Borylenen [12] und Diborenen, [13] die formal B(I)-Verbindungen und damit sehr elektronenreich sind. Beispielsweise wurde die 1,3,2-Benzodiazaborolyl-Gruppe von Weber,F ox, Marder und Mitarbeitern als Donor in konjugierten Donor-Akzeptor-Systemen verwendet (siehe Abbildung 1).…”

“…Beispielsweise wurde die 1,3,2-Benzodiazaborolyl-Gruppe von Weber,F ox, Marder und Mitarbeitern als Donor in konjugierten Donor-Akzeptor-Systemen verwendet (siehe Abbildung 1). [11] Die Gruppe um Braunschweig beschäftigt sich seit einigen Jahren mit der Entwicklung niedervalenter Borverbindungen, nämlich mit Borylenen [12] und Diborenen, [13] die formal B(I)-Verbindungen und damit sehr elektronenreich sind. Die hochenergetischen HOMOs dieser Moleküle führen typischerweise zu kleinen HOMO-LUMO-Abständen und zu einer Absorption (und manchmal Emission) im sichtbaren Bereich, selbst ohne explizite Akzeptorgruppen.…”