doi:10.1021/acs.cgd.7b00662engFuertes, S.Chueca, A.J.Martín, A.Sicilia, V.Pt2Tl Building Blocks for Two-Dimensional Extended Solids: Synthesis, Crystal Structures, and LuminescenceART-2017-100783The ß-diketonate compounds of Pt(II), [Pt(R-C^C*)(acac)] (acacH = acetylacetone, R-CH^C* = 1-(4-cyanophenyl)-3-methyl-1H-imidazol-2-ylidene (NC-CH^C*) 1A, 1-(4-(ethoxycarbonyl)phenyl)-3-methyl-1H-imidazol-2-ylidene (CO2Et-CH^C*) 1B, 1-(3, 5-dichlorophenyl)-3-methyl-1H-imidazol-2-ylidene (Cl-CH^C*) 1C) containing cyclometalated N-heterocyclic carbenes were synthesized from compounds [{Pt(µ-Cl)(R-C^C*)}2] (R = CN A, CO2Et B, Cl C). Compound C was prepared for the first time following a step-by-step protocol used to synthesize A and B. The X-ray structures of complexes 1B and 1C show that only in 1B the molecules stack in pairs through intermolecular Pt···Pt (3.370 Å) and p-p (~3.43 Å) interactions between the NHC ligand and the acac. The reaction of compounds 1A-1C with TlPF6 (2:1 molar ratio) leads to the clusters [{Pt(R-C^C*)(acac)}2Tl]+ (R = CN 2A, CO2Et 2B, Cl 2C), which exhibit a "Pt2Tl" sandwich structure, where two slightly distorted square planar "Pt(R-C^C*)(acac)" subunits are bonded to a Tl(I) center through donor-acceptor Pt-Tl bonds. Compounds 2A and 2B show an extended two-dimensional lattice in the solid state through intermolecular Pt··Pt and Tl-E (E = N, O) interactions; meanwhile 2C forms discrete molecules without any kind of intermolecular interaction among them. The effects of the R substituent and the Pt-Tl interactions on the crystal structures and the photophysical properties have been investigated.2017http://zaguan.unizar.es/record/14833610.1021/acs.cgd.7b00662http://zaguan.unizar.es/record/148336oai:zaguan.unizar.es:148336info:eu-repo/grantAgreement/ES/DGA/E21info:eu-repo/grantAgreement/ES/MINECO-FEDER/CTQ2015-67461-PCRYSTAL GROWTH & DESIGN 17, 8 (2017), 4336-4346All rights reservedhttp://www.europeana.eu/rights/rr-f/info:eu-repo/semantics/openAccess