biostudies-literatureQin JNatural Science Foundation of Guangxi Province (Guangxi Natural Science Foundation)National Natural Science Foundation of China (National Science Foundation of China)413https://www.ebi.ac.uk/biostudies/studies/S-EPMC12748632biostudies-literatureUnknown8(1)Stereoselective synthesis of cis- and trans- configurations remain challenging in molecular systems. Here, asymmetric 90<sup>o</sup> Pt(II) acceptors enable stereoselective coordination-driven self-assembly of configuration-specific [Pt<sub>2</sub>L<sub>2</sub>] metallacycles. The coordination of trimethylphosphine or triethylphosphine (PR<sub>3</sub>) and phosphangulene (Phang) to the Pt(II) centers yielded two asymmetric cis-PtCl<sub>2</sub>(PR<sub>3</sub>)(Phang) complexes. Upon ligand exchange, these acceptors assemble with the bispyridyl ligands to form statistical mixtures of cis- and trans- metallacycles. Stereoselective self-assembly is achieved by modifying the bis-pyridyl ligand with N-ortho-bismethyl groups, leveraging intramolecular C-H···π interactions with Phang, steric effecCommunications chemistryStereoselective self-assembly of cis- and trans- [Pt<sub>2</sub>L<sub>2</sub>] metallacycles via geometrically-asymmetric 90<sup>o</sup> Pt(II) acceptors.PMC127486322230105023GXNSFBA026318Tan LWang MLiao YLi DQin JLiu TWang YBai HLiu WfalseStereoselective self-assembly of cis- and trans- [Pt<sub>2</sub>L<sub>2</sub>] metallacycles via geometrically-asymmetric 90<sup>o</sup> Pt(II) acceptors.Stereoselective synthesis of cis- and trans- configurations remain challenging in molecular systems. Here, asymmetric 90<sup>o</sup> Pt(II) acceptors enable stereoselective coordination-driven self-assembly of configuration-specific [Pt<sub>2</sub>L<sub>2</sub>] metallacycles. The coordination of trimethylphosphine or triethylphosphine (PR<sub>3</sub>) and phosphangulene (Phang) to the Pt(II) centers yielded two asymmetric cis-PtCl<sub>2</sub>(PR<sub>3</sub>)(Phang) complexes. Upon ligand exchange, these acceptors assemble with the bispyridyl ligands to form statistical mixtures of cis- and trans- metallacycles. Stereoselective self-assembly is achieved by modifying the bis-pyridyl ligand with N-ortho-bismethyl groups, leveraging intramolecular C-H···π interactions with Phang, steric effec2025-01-01T00:00:00Z2025 Nov2026-06-06T09:17:17.907Z2026-05-28T03:11:55.225ZS-EPMC127486324127218410.1038/s42004-025-01803-9