Modulation of Metallophilic and π-π Interactions in Platinum Cyclometalated Luminophores with Halogen Bonding.

Luminescent cyclometalated complexes [M(C^N^N)CN] (M=Pt, Pd; HC^N^N=pyridinyl- (M=Pt 1, Pd 5), benzyltriazolyl- (M=Pt 2), indazolyl- (M=Pt 3, Pd 6), pyrazolyl-phenylpyridine (M=Pt 4)) decorated with cyanide ligand, have been explored as nucleophilic building blocks for the construction of halogen-bonded (XB) adducts using IC F as an XB donor. The negative electrostatic potential of the CN group afforded CN⋅⋅⋅I noncovalent interactions for platinum complexes 1-3; the energies of XB contacts are comparable to those of metallophilic bonding according to QTAIM analysis. Embedding the chromophore units into XB adducts 1-3⋅⋅⋅IC F has little effect on the charge distribution, but strongly affects Pt⋅⋅⋅Pt bonding and π-stacking, which lead to excited states of MMLCT (metal-metal-to-ligand charge transfer) origin.

Direct Base-Assisted C‒H Cyclonickelation of 6-Phenyl-2,2'-bipyridine.

The organonickel complexes [Ni(Phbpy)X] (X = Br, OAc, CN) were obtained for the first time in a direct base-assisted arene C(sp)-H cyclometalation reaction from the rather unreactive precursor materials NiX and HPhbpy (6-phenyl-2,2'-bipyridine) or from the versatile precursor [Ni(HPhbpy)Br]. Different from previously necessary C‒Br oxidative addition at Ni(0), an extended scan of reaction conditions allowed quantitative access to the title compound from Ni(II) on synthetically useful timescales through base-assisted C‒H activation in nonpolar media at elevated temperature. Optimisation of the reaction conditions (various bases, solvents, methods) identified 1:2 mixtures of acetate and carbonate as unrivalled synergetic base pairs in the optimum protocol that holds promise as a readily usable and easily tuneable access to a wide range of direct nickelation products.

Improvement of the Photophysical Performance of Platinum-Cyclometalated Complexes in Halogen-Bonded Adducts.

Three groups of luminescent platinum complexes [Pt(C^N)(L)(Y)] [C^N=benzothienyl-pyridine (1), bezofuryl-pyridine (2), phenyl-pyridine (3); L/Y=DMSO/Cl (a), PPh /Cl (b), PPh /CN (c)] have been probed as halogen-bond (XB) acceptors towards iodofluorobenzenes (IC F and I C F ). Compounds 1 a and 2 a (L/Y=DMSO/Cl) afford the adducts 1 a⋅⋅⋅I C F and 2 a⋅⋅⋅I C F , which feature I⋅⋅⋅S /I⋅⋅⋅π and I⋅⋅⋅O /I⋅⋅⋅Cl short contacts, respectively. The phosphane-cyanide derivatives 1 c and 2 c (L/Y=PPh /CN) co-crystallise with both IC F and I C F .

Cyclometalated Platinum(II) Cyanometallates: Luminescent Blocks for Coordination Self-Assembly.

A family of cyanide-bridged heterometallic aggregates has been constructed of the chromophoric cycloplatinated metalloligands and coordinatively unsaturated d fragments {M(PPh)}. The tetranuclear complexes of general composition [Pt(C^N)(CN)M(PPh)] [C^N = ppy, M = Cu (1), Ag (2); C^N = tolpy (Htolpy = 2-(4-tolyl)-pyridine), M = Cu (4), Ag (5); C^N = Fppy (HFppy = 2-(4, 6-difluorophenyl)-pyridine), M = Cu (7), Ag (8)] demonstrate a squarelike arrangement of the molecular frameworks, which is achieved due to favorable coordination geometries of the bridging ligands and the metal ions. Variation of the amount of the ancillary phosphine (for M = Ag) afforded compounds [Pt(C^N)(CN)Ag(PPh)] (C^N = ppy, 3; C^N = tolpy, 6); for the latter one an alternative cluster topology, stabilized by the Pt-Ag metallophilic and η-C(C^N)-Ag bonding, was observed.

Solid-State and Solution Metallophilic Aggregation of a Cationic [Pt(NCN)L](+) Cyclometalated Complex.

The noncovalent intermolecular interactions (π-π stacking, metallophilic bonding) of the cyclometalated complexes [Pt(NCN)L](+)X(-) (NCN = dipyridylbenzene, L = pyridine (1), acetonitrile (2)) are determined by the steric properties of the ancillary ligands L in the solid state and in solution, while the nature of the counterion X(-) (X(-) = PF6(-), ClO4(-), CF3SO3(-)) affects the molecular arrangement of 2·X in the crystal medium. According to the variable-temperature X-ray diffraction measurements, the extensive Pt···Pt interactions and π-stacking in 2·X are significantly temperature-dependent. The variable concentration (1)H and diffusion coefficients NMR measurements reveal that 2·X exists in the monomeric form in dilute solutions at 298 K, while upon increase in concentration [Pt(NCN)(NCMe)](+) cations undergo the formation of the ground-state oligomeric aggregates with an average aggregation number of ∼3.

Halogen Bonding to Amplify Luminescence: A Case Study Using a Platinum Cyclometalated Complex.

The cocrystallization of a weakly luminescent platinum complex [Pt(btpy)(PPh3)Cl](1) (Hbtpy=2-(2benzothienyl)pyridine; emission quantum yield Φem=0.03) with fluorinated bromo- and iodoarenes C6F6-nXn (X=Br, I; n=1, 2) results in the formation of efficient halogen-bonding (XB) interactions Pt-Cl⋅⋅⋅X-R. An up to 22-fold enhancement (Φem =0.

Alkynyl triphosphine copper complexes: synthesis and photophysical studies.

A rigid triphosphine PPh2C6H4-PPh-C6H4PPh2 () reacted with Cu(+) and a stoichiometric amount of terminal alkyne under basic conditions to give a family of copper(i) alkynyl compounds [Cu()C[triple bond, length as m-dash]CR]. The number of terminal -C[triple bond, length as m-dash]CH groups in the starting ligand determines the nuclearity of the resulting complexes giving mono- (, R = Ph; , R = C6H4OMe; , R = C6H4NO2; , R = C6H4CF3; , R = 2-pyridyl), di- (R = -(C6H4)n-, n = 1 (), n = 2, (), n = 3 ()) and trinuclear complexes (, R = 1,3,5-(C6H4)3-C6H3; , R = 1,3,5-(C6H4-4-C2C6H4)3-C6H3). In all the complexes the Cu(i) centers are found in a distorted tetrahedral environment that is achieved by tridentate coordination of the ligand and σ-bonding to the alkynyl function.