TY - JOUR
T1 - Anion coordination in metal-organic frameworks functionalized with urea hydrogen-bonding groups
AU - Custelcean, Radu
AU - Moyer, Bruce A.
AU - Bryantsev, Vyacheslav S.
AU - Hay, Benjamin P.
PY - 2006/2
Y1 - 2006/2
N2 - A series of metal-organic frameworks (MOFs) functionalized with urea hydrogen-bonding groups has been synthesized and structurally analyzed by single-crystal X-ray diffraction to evaluate the efficacy of anion coordination by urea within the structural constraints of the MOFs. We found that urea-based functionalities may be used for anion binding within metal-organic frameworks when the tendency for urea⋯urea self-association is decreased by strengthening the intramolecular CH⋯O hydrogen bonding of N-phenyl substituents to the carbonyl oxygen atom. Theoretical calculations indicate that N,N′-bis(m-pyridyl)urea (BPU) and N,N′-bis(m-cyanophenyl)urea (BCPU) should have enhanced hydrogen-bonding donor abilities toward anions and decreased tendencies to self-associate into hydrogen-bonded tapes compared to other disubstituted ureas. Accordingly, BPU and BCPU were incorporated in MOFs as linkers through coordination of various Zn, Cu, and Ag transition metal salts, including Zn(ClO4)2, ZnSO4, Cu(NO 3)2, Cu(CF3SO3)2, AgNO3, and AgSO3CH3. Structural analysis by single-crystal X-ray diffraction showed that these linkers are versatile anion binders, capable of chelate hydrogen bonding to all of the oxoanions explored. Anion coordination by the urea functionalities was found to successfully compete with urea self-association in all cases except for that of charge-diffuse perchlorate.
AB - A series of metal-organic frameworks (MOFs) functionalized with urea hydrogen-bonding groups has been synthesized and structurally analyzed by single-crystal X-ray diffraction to evaluate the efficacy of anion coordination by urea within the structural constraints of the MOFs. We found that urea-based functionalities may be used for anion binding within metal-organic frameworks when the tendency for urea⋯urea self-association is decreased by strengthening the intramolecular CH⋯O hydrogen bonding of N-phenyl substituents to the carbonyl oxygen atom. Theoretical calculations indicate that N,N′-bis(m-pyridyl)urea (BPU) and N,N′-bis(m-cyanophenyl)urea (BCPU) should have enhanced hydrogen-bonding donor abilities toward anions and decreased tendencies to self-associate into hydrogen-bonded tapes compared to other disubstituted ureas. Accordingly, BPU and BCPU were incorporated in MOFs as linkers through coordination of various Zn, Cu, and Ag transition metal salts, including Zn(ClO4)2, ZnSO4, Cu(NO 3)2, Cu(CF3SO3)2, AgNO3, and AgSO3CH3. Structural analysis by single-crystal X-ray diffraction showed that these linkers are versatile anion binders, capable of chelate hydrogen bonding to all of the oxoanions explored. Anion coordination by the urea functionalities was found to successfully compete with urea self-association in all cases except for that of charge-diffuse perchlorate.
UR - http://www.scopus.com/inward/record.url?scp=32644453286&partnerID=8YFLogxK
U2 - 10.1021/cg0505057
DO - 10.1021/cg0505057
M3 - Article
AN - SCOPUS:32644453286
SN - 1528-7483
VL - 6
SP - 555
EP - 563
JO - Crystal Growth and Design
JF - Crystal Growth and Design
IS - 2
ER -