Precisely controlling the coordination microenvironment and electronic features of polynuclear secondary building units (SBUs) in coordination polymers (CPs) is an efficient approach to governing their fundamental performance. Here, different multinuclear SBUs (binuclear, trinuclear, and pentanuclear SBUs for 1–3, respectively) were introduced into Cd-based CPs, which were used as frictional electrode materials, to clarify the contributions of polynuclear Cd-SBUs through the output of triboelectric nanogenerators (TENGs). The results demonstrated that 1-TENG with binuclear Cd-SBUs possessed the highest output, whereas 3-TENG with the pentanuclear Cd-SBUs indicated the minimum output, suggesting that the binuclear Cd-SBUs in 1 lost electrons most readily and generated much more charge, which was further confirmed by density functional theory calculations. This work opened a new prospect to confirm the gaining/losing capability of polynuclear Cd-SBUs in CPs and provided an effective approach to tuning both the stability and functionality of polynuclear CPs as frictional pair materials to regulate the output of CPs-based TENGs.

A main difficulty in C−H bond functionalization is to undertake the catalyst control accurately where the reaction takes place. In this work, to achieve highly effective and regioselective single-site catalysts, a three-dimensional (3D) rhombus-like framework of {[Mn(Hidbt)DMF]•H 2 O} n (1) [H 3 idbt = 5,5′-(1H-imidazole-4,5diyl)-bis(2H-tetrazole)] containing coordinated DMF molecules was constructed. For the dissolution−recrystallization structural transformation process, attractive structural transformations proceeded f r o m 1 t o a n e w c r y s t a l l i n e s p e c i e s f o r m u l a t e d a s {[Mn 3 (idbt) 2 (H 2 O) 2 ]•3H 2 O} n (2) with a 3D windowlike architecture, and then the Mn ions in 2 could be exchanged with Cu ions through cation exchange in a single-crystal to single-crystal fashion to produce the Cu-exchanged product {[Mn 2 Cu(idbt) 2 (H 2 O) 2 ]•3H 2 O} n (2a), which had a windowlike framework like that of 2. Furthermore, 2 and 2a were used as heterogeneous catalysts for the regioselective C−H halogenation of phenols with N-halosuccinimides (NCS and NBS) to produce the site selective single monohalogenated products. It was found that the catalytic activity and site selectivity of 2a were much higher than those of 2, because the unique structural features of 2a with the uniformly dispersed Cu II active centers served as a single-site catalyst with a site-isolated and well-defined platform to promote the C−H halogenation reaction in regiocontrol and guide an orientation that favored the para selectivity during the reaction process.

The continuous and uniform MOF-based membrane (1a) as a highly efficient heterogeneous catalyst was fabricated on porous Cu foam to significantly outperform bulk crystals 1 to execute C–H hydroxyalkynylation reactions with regiocontrol.

Nanoscale 1 and 2 with the benefit of readily accessible active sites had shown to be more effective heterogeneous catalysts than large sizes of 1 and 2 to execute tandem conversion reactions of nitromethylbenzenes into benzolic acids frameworks.

Tuning the morphology and size of coordination polymers (CPs) is an effective strategy to enable crystalline materials for desired applications. Herein, two CPs, named as [Cd2(DBTP)(H2O)2]n (1) and {[Zn2(DBTP)(H2O)]·2.5H2O}n (2),...