TY - JOUR
T1 - Stepwise transformation of the molecular building blocks in a porphyrin-encapsulating metal-organic material
AU - Zhang, Zhenjie
AU - Wojtas, Lukasz
AU - Eddaoudi, Mohamed
AU - Zaworotko, Michael J.
PY - 2013/4/24
Y1 - 2013/4/24
N2 - When immersed in solutions containing Cu(II) cations, the microporous metal-organic material P11 ([Cd4(BPT)4]·[Cd(C 44H36N8)(S)]·[S], BPT = biphenyl-3,4′,5-tricarboxylate) undergoes a transformation of its [Cd 2(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 Cd2+/Cu2+ 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.
AB - When immersed in solutions containing Cu(II) cations, the microporous metal-organic material P11 ([Cd4(BPT)4]·[Cd(C 44H36N8)(S)]·[S], BPT = biphenyl-3,4′,5-tricarboxylate) undergoes a transformation of its [Cd 2(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 Cd2+/Cu2+ 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.
UR - http://www.scopus.com/inward/record.url?scp=84876727742&partnerID=8YFLogxK
U2 - 10.1021/ja4015666
DO - 10.1021/ja4015666
M3 - Article
AN - SCOPUS:84876727742
SN - 0002-7863
VL - 135
SP - 5982
EP - 5985
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
IS - 16
ER -