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

Zhenjie Zhang
, Lukasz Wojtas
, Mohamed Eddaoudi
, Michael J. Zaworotko

Research output: Contribution to journal › Article › peer-review

Abstract

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.

Original language	English
Pages (from-to)	5982-5985
Number of pages	4
Journal	Journal of the American Chemical Society
Volume	135
Issue number	16
DOIs	https://doi.org/10.1021/ja4015666
Publication status	Published - 24 Apr 2013
Externally published	Yes

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@article{8ee0157984024f268e8658c9c765ab41,

title = "Stepwise transformation of the molecular building blocks in a porphyrin-encapsulating metal-organic material",

abstract = "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.",

author = "Zhenjie Zhang and Lukasz Wojtas and Mohamed Eddaoudi and Zaworotko, \{Michael J.\}",

year = "2013",

month = apr,

day = "24",

doi = "10.1021/ja4015666",

language = "English",

volume = "135",

pages = "5982--5985",

journal = "Journal of the American Chemical Society",

issn = "0002-7863",

number = "16",

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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 - https://www.scopus.com/pages/publications/84876727742

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 -

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

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