Herein we report three new gold(i) complexes with a benzothiazole-2,7-fluorenyl moiety bound through a gold–carbon σ-bond and either an N-heterocyclic carbene or organophosphine as ancillary ligands.

Template directed synthesis of metal–organic frameworks (MOFs) is of increasing interest. Herein we report the synthesis of six new MOFs synthesized from 2,5-thiophenedicarboxylic acid (TDC) and InCl3. The new frameworks are formally two- (YCM-21) and one-dimensional (YCM-22) anionic, as well as three-dimensional neutral (YCM-23). YCM-22 contains an unprecedented dianionic [InCl3(κ2-O2CAr)2]2– node. The structural diversity represented by these materials is entirely controlled by addition of organic ammonium salts during the synthesis process. The role of the additives is briefly discussed with observed correlations of (1) hydrogen bonding and cation−π interactions influencing MOF dimensionality and (2) the presence of anionic chlorides creating a chlorine-rich metal center leading to a one-dimensional framework.

The syntheses and photophysical characterization of five new gold(I) complexes bearing diphenylamine-substituted fluorenyl moieties are reported; four are characterized by X-ray diffraction crystallography. Ancillary ligation on gold(I) is provided by organophosphine and N-heterocyclic carbene ligands. Two complexes, Au-DPA0 and Au-DPA1, are σ-aryls, two, Au-ADPA0 and Au-ADPA1, are σ-alkynyls, and one, Au-TDPA1, is a σ-triazolyl bound through carbon. All complexes show vibronically structured absorption and luminescence bands that are assignable to π−π* transitions localized on the diphenylamine-substituted fluorenyl π system. The excited-state dynamics of all five chromophores are governed by selection of the ancillary ligand and σ attachment of the diphenylamine-substituted fluorenyl moiety. All of these chromophores are dual luminescent in a toluene solution at 298 K. The luminescence from the aryl derivatives, Au-ADPA0 and Au-DPA1, appears green. The alkynyl derivative containing a phosphine ancillary ligand, Au-ADPA0, is a white-light emitter, while the alkynyl derivative containing an N-heterocyclic carbene ancillary ligand, Au-ADPA1, is a yellow-light emitter. The luminescence from the triazolyl-linked chromophore, Au-TDPA1, appears as yellow-green. Spin-restricted density functional theory calculations support the assignments of ligand-centric optical transitions but with contributions of ligand-to-metal charge transfer involving the vacant Au 6p orbital.

Three new gold(i) alkynyl complexes containing a benzothiazole fluorenyl ligand were prepared. Their photophysical properties are compared with previously published dinuclear and mononuclear gold(i) aryl complexes with the same chromophoric ligand.