Stepwise transformation of the molecular building blocks in a porphyrin-encapsulating metal-organic material

Zhenjie Zhang; Lukasz Wojtas; Mohamed Eddaoudi; Michael J Zaworotko

doi:10.1021/ja4015666

Stepwise transformation of the molecular building blocks in a porphyrin-encapsulating metal-organic material

J Am Chem Soc. 2013 Apr 24;135(16):5982-5. doi: 10.1021/ja4015666. Epub 2013 Apr 10.

Authors

Zhenjie Zhang¹, Lukasz Wojtas, Mohamed Eddaoudi, Michael J Zaworotko

Affiliation

¹ Department of Chemistry, University of South Florida, 4202 East Fowler Avenue, CHE205, Tampa, Florida 33620, USA.

PMID: 23547653
DOI: 10.1021/ja4015666

Abstract

When immersed in solutions containing Cu(II) cations, the microporous metal-organic material P11 ([Cd4(BPT)4]·[Cd(C44H36N8)(S)]·[S], BPT = biphenyl-3,4',5-tricarboxylate) undergoes a transformation of its [Cd2(COO)6](2-) molecular building blocks (MBBs) into novel tetranuclear [Cu4X2(COO)6(S)2] MBBs to form P11-Cu. The transformation occurs in single-crystal to single-crystal fashion, and its stepwise mechanism was studied by varying the Cd(2+)/Cu(2+) ratio of the solution in which crystals of P11 were immersed. P11-16/1 (Cd in framework retained, Cd in encapsulated porphyrins exchanged) and other intermediate phases were thereby isolated and structurally characterized. P11-16/1 and P11-Cu retain the microporosity of P11, and the relatively larger MBBs in P11-Cu permit a 20% unit cell expansion and afford a higher surface area and a larger pore size.