Intermolecular (Isocyano group)···PtII interactions involving coordinated isocyanides in cyclometalated PtII complexes

Luminescent Anionic Cyclometalated Organoplatinum (II) Complexes with Terminal and Bridging Cyanide Ligand: Structural and Photophysical Properties

“…In this context, coordination of strong field auxiliary ligands are desirable. The effect of the coordination by pentafluorophenyl, − alkynyl (CCR), , and isocyanide (CNR) ,− as auxiliary ligands in heteroleptic cyclometalated [Pt­(C^N)­L 2 ] n ( n = −1, 0, and +1) complexes have been explored by us and others, and some of these complexes have been proven to be excellent building blocks for the preparation of clusters, ,, and extended aggregates , with intriguing optical properties. − Cyanide is another important strong field ligand with very strong σ-donor ability, which has been widely exploited not only in the Pt­(II) chemistry but also with other d 6 metal ions to form complexes that emit efficient blue phosphorescence. − Furthermore, in accordance with the well-stablished capability of the cyanide ligand to act as a compact bridging ligand, some of these complexes have been successfully exploited to construct heteropolynuclear complexes in triangular, square, and hexagonal forms featuring bridging ligands or additionally stabilized by metallophillic interactions, which have attractive optical properties. In recent years, dicyanide cycloplatinated anionic units have been employed to form soft salts [Pt­(C^N)­(en)]­[Pt­(C^N)­(CN) 2 ] (en = ethylenediamine) exhibiting interesting reversible excitation-wavelength-dependent behavior owing to the modulation of the Pt­(II)···Pt­(II) bond interaction by means of mechanical and vapor fuming .…”

Chameleonic metal-bound isocyanides: a π-donating CuI-center imparts nucleophilicity to the isocyanide carbon toward halogen bonding

“…In particular, the isocyanide ligand C atom in Pt II and Pd II complexes exhibit an electrophilic character and is involved in noncovalent π-(C)-hole⋯(lone pair), 45 46,47 and π-(C)-hole⋯π 48 contacts (Scheme 1, right panel). Notably, other coordinated species featuring various triple-bonds (e.g., carbon monoxide, [49][50][51] nitriles, 52 and dialkylcyanamides 53 ) also exhibit an electrophilicity in noncovalent interactions.…”

“…In particular, the isocyanide ligand C atom in Pt II and Pd II complexes exhibit an electrophilic character and is involved in noncovalent π-(C)-hole⋯(lone pair), 45 π-(C)-hole⋯d z 2 -[M], 46,47 and π-(C)-hole⋯π 48 contacts (Scheme 1, right panel). Notably, other coordinated species featuring various triple-bonds ( e.g.…”

Polymorph-Dependent Phosphorescence of Cyclometalated Platinum(II) Complexes and Its Relation to Non-covalent Interactions

“…These non-covalent linkages can significantly alter both ground and excited-state properties of Pt II -based systems and, hence, photophysical parameters. 20 , 27 − 31 …”

“…In contrast to octahedral d 6 -Ru II and d 6 -Ir III complexes, d 8 -Pt II -based species usually adopt a square-planar coordination geometry with open axial coordination sites facilitating non-covalent binding to Pt II centers. These non-covalent linkages can significantly alter both ground and excited-state properties of Pt II -based systems and, hence, photophysical parameters. ,− …”