Inspection of the X‐ray structures of the newly prepared trans‐[MII(CNXyl)2(DAPT)2]Cl(BF4) (M=Pd, Pt; Xyl=2,6‐Me2C6H3; DAPT=4,6‐diaminopyrimidine‐2(1H)‐thione) complexes and the appropriate Hirshfeld molecular surface analysis allowed the recognition of the previously unknown π‐hole⋅⋅⋅metal interactions between a ligated isocyano group (acting as a π‐hole donor) and the positively charged d8‐PtII and d8‐PdII metal centers (acting as nucleophiles); this is the first identification of π‐hole⋅⋅⋅metal interactions with triple‐bond species. Results of DFT calculations followed by the topological analysis of the electron density distribution within the framework of Bader's theory (quantum theory of atoms in molecules, QTAIM) confirmed the presence of these contacts. The electrostatic surface potential calculations indicated that π‐hole⋅⋅⋅metal contacts are formed upon interaction between the electrophilic isocyano C atom (π‐hole donor) and the nucleophilic dz2 orbital of the metal centers, which act as π‐hole acceptors. Available CCDC data were processed from the perspective of the π‐hole⋅⋅⋅metal interactions with isocyanide ligands, and their analysis disclosed the role of metal nucleophilicity in the corresponding π‐hole acceptor ability.

Both carbon and nitrogen centers in the coordinated isocyano group are capable of acting as a π-hole donor toward lone pairs.

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Reaction of the palladium(II) and platinum(II) isocyanide complexes cis-[MCl 2 (CNR) 2 ] [M = Pd, R = C 6 H 3 (2,6-Me 2 ) (Xyl), 2-Cl-6-MeC 6 H 3 , cyclohexyl (Cy), t-Bu, C(Me) 2 CH 2 (Me) 3 (1,1,3,3-tetramethylbuth-1-yl abbreviated as tmbu); M = Pt, R = Xyl, 2-Cl-6-MeC 6 H 3 , Cy, t-Bu, and tmbu] with N,N′-diphenylguanidine (DPG) leads to DPG-derived metal-bound deprotonated acyclic diaminocarbene (ADC) species. This reaction occurs via a two-step process, involving the initial coupling of the guanidine with one of the isocyanides and leading to deprotonated monocarbene monochelated species, while the next addition grants the deprotonated bis-carbene bis-chelated metal compounds. DPG behaves as nucleophile, deprotonating base, and chelator. The addition of DPG proceeded with different regioselectivity depending on the metal center and, in a larger extent, on the substituent R in RNCs. The X-ray diffraction studies for the deprotonated mono-and bis-carbene complexes confirmed the regioisomerism of these species and allowed the identification of ADC protolytic forms stabilized in the solid-state. 1D ( 1 H and 13 C{ 1 H}) and 2D ( 1 H, 1 H-NOESY; 1 H, 15 N-HSQC; 1 H, 15 N-HMBC) solution NMR of the obtained systems demonstrated their configuration isomerism accompanied by prototropic tautomerism. Together, the solid-state and solution data provide an insight into the flexible character of ADC species.

C–X⋯Cl–Pt Halogen bonds and πh⋯dz2[PtII] contacts led to the 2-fold increase of phosphorescence quantum yields for [cyclometalated]-PtII(isocyanide) complexes upon co-crystallisation with halosubstituted perfluorinated arenes.

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A novel series of cyclometalated platinum(II) complexes bearing acyclic diaminocarbene (ADC) ancillary ligands was designed and prepared. Their photophysical properties were systematically studied through experimental and theoretical investigations. All complexes...