TY - JOUR
T1 - Multi-Ferrocene-Containing Silanols as Redox-Active Anion Receptors
AU - Bruña, Sonia
AU - Garrido-Castro, Alberto F.
AU - Perles, Josefina
AU - Montero-Campillo, M. Merced
AU - Mó, Otilia
AU - Kaifer, Angel E.
AU - Cuadrado, Isabel
N1 - Funding Information:
The authors are grateful to the Spanish Ministerio de Economia y Competitividad (MINECO) (projects CTQ2012-30728, CTQ2015-63997-C2-1-P, and CTQ2013-43698-P) for the generous support of this work. M.M.M.-C. and O.M. thank the STSM COST Action CM1204 and the Project FOTOCARBON-CM S2013/MIT-2841 of the Comunidad Autonoma de Madrid. Computational time at Centro de Computacion Cientifca (CCC) of Universidad Autonoma de Madrid is acknowledged. A.E.K. acknowledges the support from the National Science Foundation (CHE-1412455).
Publisher Copyright:
© 2016 American Chemical Society.
PY - 2016/10/24
Y1 - 2016/10/24
N2 - The ability of diferrocenylsilanediol, Fc2Si(OH)2 (5), and 1,1,3,3-tetraferrocenyldisiloxane-1,3-diol, Fc2(HO)Si-O-Si(OH)Fc2 (6), to act as new electroactive anion receptors for either acetate or chloride anions has been investigated in solution, in the solid state, and in the gas phase. 1H NMR spectroscopic titrations with anions reveal that the binding interaction causes chemical-shift perturbations not only in the Si-OH hydrogen-bonding donor motif but also in the ferrocenyl protons of receptors 5 and 6. Square-wave voltammetric studies evidence that multiferrocenyl silanols 5 and 6 exhibit higher ability for electrochemical sensing of acetate than chloride, since the corresponding half-wave potentials (E1/2) for the successive ferrocene oxidations display a higher cathodic shift in the presence of such an anion. Furthermore, single-crystal X-ray diffraction analyses of the tetrabutylammonium salts of complexes [Fc2Si(OH)2·CH3COO]- (8), [Fc2Si(OH)2·Cl]- (9), [Fc2(HO)Si-O-Si(OH)Fc2·CH3COO]- (10), [{Fc2(HO)Si-O-Si(OH)Fc2}2·CH3COO]- (11), and [Fc2(HO)Si-O-Si(OH)Fc2·Cl]- (12) confirm that redox-active silanol receptors 5 and 6 can bind the acetate and chloride anions in the solid state. Electronic structure calculations were carried out for 5 to explore the intrinsic ability of the silanediol group to bind these anions in a vacuum.
AB - The ability of diferrocenylsilanediol, Fc2Si(OH)2 (5), and 1,1,3,3-tetraferrocenyldisiloxane-1,3-diol, Fc2(HO)Si-O-Si(OH)Fc2 (6), to act as new electroactive anion receptors for either acetate or chloride anions has been investigated in solution, in the solid state, and in the gas phase. 1H NMR spectroscopic titrations with anions reveal that the binding interaction causes chemical-shift perturbations not only in the Si-OH hydrogen-bonding donor motif but also in the ferrocenyl protons of receptors 5 and 6. Square-wave voltammetric studies evidence that multiferrocenyl silanols 5 and 6 exhibit higher ability for electrochemical sensing of acetate than chloride, since the corresponding half-wave potentials (E1/2) for the successive ferrocene oxidations display a higher cathodic shift in the presence of such an anion. Furthermore, single-crystal X-ray diffraction analyses of the tetrabutylammonium salts of complexes [Fc2Si(OH)2·CH3COO]- (8), [Fc2Si(OH)2·Cl]- (9), [Fc2(HO)Si-O-Si(OH)Fc2·CH3COO]- (10), [{Fc2(HO)Si-O-Si(OH)Fc2}2·CH3COO]- (11), and [Fc2(HO)Si-O-Si(OH)Fc2·Cl]- (12) confirm that redox-active silanol receptors 5 and 6 can bind the acetate and chloride anions in the solid state. Electronic structure calculations were carried out for 5 to explore the intrinsic ability of the silanediol group to bind these anions in a vacuum.
UR - http://www.scopus.com/inward/record.url?scp=84992735197&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=84992735197&partnerID=8YFLogxK
U2 - 10.1021/acs.organomet.6b00559
DO - 10.1021/acs.organomet.6b00559
M3 - Article
AN - SCOPUS:84992735197
VL - 35
SP - 3507
EP - 3519
JO - Organometallics
JF - Organometallics
SN - 0276-7333
IS - 20
ER -