Citation for published item:eerD vF nd uhlertD tF nd frokhinkeD F nd f¤ ohlingD vF nd rlmD tF nd frokhinkeD eF nd tmmlerD rFEtF nd xeumnnD fF nd xerviD gF nd rrderD FeF nd poxD wFeF @PHIQA 9gDgEfis@enzodizorolylAdirElosoEdodeornes X synthesisD struturesD photophysis nd eletrohemistryF9D hlton trnstionsFD RP @QHAF ppF IHWVPEIHWWTF 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.

The reaction of the N-lithiated 3,6-di-tert-butyl-carbazole (2) with 2-bromo-1,3-diethyl-1,3,2-benzodiazaborole (1a) and 2-bromo-1,3-diphenyl-1,3,2-benzodiazaborole (1b) afforded the 2-N-carbazolyl-functionalized benzodiazaboroles 3a and 3b as colourless solids in 77 and 73 % yield, respectively. Synthesis of 2[5Ј-N-carbazolyl-2Ј-thienyl]-1,3-diethyl-1,3,2-benzodiazaborole (5a) was effected by lithiation of N-(2-thienyl)carbazole (4) and subsequent reaction with equimolar amounts of 1a, and 5a was obtained in 68 % yield. Similarly,

The reaction of the N-lithiated 3,6-di-tert-butylcarbazole with fluorodimesitylborane afforded the N-carbazolyl-functionalized dimesitylborane 1 as a colorless solid in 70 % yield.[4-(3,6-Di-tert-butylcarbazol-9-yl)phenyl]dimesitylborane (2) was synthesized in 59 % yield by the lithiation of N-(4-bromophenyl)-3,6-di-tert-butylcarbazole and the subsequent treatment of the organolithium compound with fluorodimesitylborane. Synthesis of yellow crystalline [5-(carbazol-9-yl)-2-thienyl]dimesitylborane 3 was effected in 66 % yield by the lithiation of 3,6-di-tert-butyl-N-(2-thienyl)carbazole and the subsequent reaction with fluorodimesitylborane. Coupling of N-(4-bromophenyl)-3,6-di-tert-butylcarbazole and 2-bromo-1,3-diethyl-1,3,2-benzodiazaborole with magnesium metal in

Reactions of equimolar amounts of dicyclohexylborane (DCB) with a series of 2‐alkynyl‐1,3‐diethyl‐1,3,2‐benzodiazaboroles R–C≡C–B(NEt)2C6H4 (1: R = nBu, 2: R = tBu, 3: R = Ph, 4: R = p‐Me2NC6H4, 5: R = p‐MeOC6H4) regioselectively afforded the 1,1‐diborylalkenes (Z)‐R(H)C=C{(B{NEt}2C6H4)B(c‐C6H11)2} (7a–11a) as the result of a cis‐addition of the BH bond of the borane to the C≡C triple bond in compounds 1 to 5. In contrast to this, reaction of Me3Si–C≡C–B(NEt)2C6H4 (6) with HB(c‐C6H11)2 yielded a 2.5:1 mixture of the 1,2‐diborylated alkene (Z)‐Me3Si{(c‐C6H11)2B}C=CHB(NEt)2C6H4 (12b) and the 1,1‐regioisomer (Z)‐Me3Si(H)C=C{B(NEt)2C6H4}{B(c‐C6H11)2} (12a). These results were rationalized by the differing π‐acceptor qualities of the benzodiazaborolyl and trimethylsilyl substituents at the C≡C triple bond in compounds 1 to 6. The novel products 7–12 were characterized by elemental analysis, mass spectrometry and NMR spectroscopy (1H, 11B, and 13C NMR). The molecular structures of 9b and 12b were substantiated by single‐crystal X‐ray diffraction analysis.

Keywords: Boron / Diazaboroles / Perfluoroaryls / Photophysics / LuminescenceThe reaction of N- 4Ј-trimethylsilylphenyl-3,6-di-tert-butylcarbazole (3) or N-5Ј-trimethylsilylthien-2Ј-yl-3,6-di-tert-butylcarbazole (4) with boron tribromide and subsequently with triphenylphosphane afforded the dibromoborylphenylcarbazole-phosphane adduct 5 or its thiophene derivative 6 as colorless solids. These adducts were converted into the new benzodiazaborole derivatives 7 and 8 by treatment with N,NЈ-bis(pentafluorophenyl)-o-phenylenediamine (1) and 2,2,6,6-tetramethylpiperidine in hot toluene (52 or 45 % [a]4268 yield). The analogous compounds 9 and 10 were obtained by condensing precursors 5 and 6 with bis(N,NЈ-2,3,5,6-tetrafluoropyrid-4-yl)-o-phenylenediamine (2) in the presence of the piperidine derivative in 35 and 16 % yield. Compounds 7-10 were characterized by NMR spectroscopy ( 1 H, 11 B, 13 C, 19 F) and mass spectrometry. The molecular structure of 8 was elucidated by X-ray diffraction analysis. The borylated systems show intense blue luminescence upon UV irradiation. 4269Scheme 2. Syntheses of o-phenylenediamines 1 and 2.Scheme 3. Syntheses of 5 and 6.