The steric strain around copper(I) in typical [Cu(NN_R)₂]⁺ complexes, where NN_R is a diimine ligand substituted in α-positions of the nitrogen atoms by R, is known to strongly impact the excited-state properties. Generally speaking, the larger the R, the longer the emission lifetime and the higher the quantum yield. However, the stability of the coordination scaffold can be at stake if the steric strain imposed by R is too large. In this work, we explore a way of fine-tuning the steric strain around Cu(I) to reach a balance between high emission quantum yield and stability in a highly bulky copper(I) complex. Taking stable [Cu(dipp)₂]⁺ and unstable [Cu(dtbp)₂]⁺ (where dipp and dtbp are, respectively, 2,9-diisopropyl-1,10-phenanthroline and 2,9-di-tert-butyl-1,10-phenanthroline) as the boundary of two least and most sterically strained structures, we designed and characterized the nonsymmetrical ligand 2-isopropyl-9-tert-butyl-1,10-phenanthroline (L1) and corresponding complex [Cu(L1)₂]⁺ (Cu1). The key experimental findings are that Cu1 exhibits a rigid tetrahedral geometry in the ground state, close to that of [Cu(dtbp)₂]⁺ and with an intermediate stability between that of [Cu(dipp)₂]⁺ and [Cu(dtbp)₂]⁺. Conversely, the nonsymmetrical nature of ligand L1 leads to a shorter emission lifetime and smaller quantum yield than those of either [Cu(dipp)₂]⁺ or [Cu(dtbp)₂]⁺. This peculiar behavior is rationalized through the in depth analysis of the ultrafast dynamics of the excited state measured with optical transient absorption spectroscopy and theoretical calculations performed on the ground and excited state of Cu1. Our main findings are that the obtained complex is significantly more stable than [Cu(dtbp)₂]⁺ despite the sterically strained coordination sphere. The nonsymmetrical nature of the ligand translates into a strongly distorted structure in the excited state. The distortion can be described as a rocking motion of one ligand, entailing the premature extinction of the excited state via several deactivation channels.

In this article, we resort to first-principles molecular dynamic simulations to examine the thermal effects on the structure of [Pb(CO)_n]²⁺ complexes. Values of n are chosen to sample structures where hemidirected (n = 2, 4 and 6) or holodirected (n = 7 and 8) structures are found when using static approaches. In all cases, highly flexible structures are observed. In particular, hemidirectional distortions are characterized using geometrical and topological analysis. The octacarbonyl complex exhibits the decoordination of one of its carbonyl ligands at 300 K.

An upper rim, o-(diphenylphosphinyl)phenyl-substituted calix[4]arene has been prepared and its coordinative properties investigated. When heated in the presence of palladium, the new biarylphosphine undergoes conversion into two diastereomeric, calixarene-fused phospholes. In both, the P lone pair adopts a fixed orientation with respect to the calixarene core. The more hindered phosphole (8), i.e. the one with the endo-oriented lone pair (cone angle 150°–175°), forms complexes having their metal centre positioned very near the calixarene unit but outside the cavity, thus inducing an unusual chemical shift of one of the methylenic ArCH₂Ar protons owing to interactions with the metal centre. As expected for dibenzophospholes, the complex [Rh(acac)(CO)·8], when combined with one equivalent of free 8, efficiently catalyses the hydroformylation of styrene, the catalytic system displaying high regioselectivity in favour of the branched aldehyde (b/l ratio up to 30). The optical and redox properties of the derivatives have also been investigated.