TY - JOUR
T1 - Article nickel(Ii)-based building blocks with schiff base derivatives
T2 - Experimental insights and dft calculations
AU - Novoa, Néstor
AU - Manzur, Carolina
AU - Roisnel, Thierry
AU - Kahlal, Samia
AU - Saillard, Jean Yves
AU - Carrillo, David
AU - Hamon, Jean René
N1 - Funding Information:
Funding: This research was funded by Fondo Nacional de Desarrollo Científico y Tecnológico [FONDECYT (Chile), grant no. 1190034, and GENCI French national computer center, Grant a0090807367.
Funding Information:
This research was funded by Fondo Nacional de Desarrollo Cient?fico y Tecnol?gico [FONDECYT (Chile), grant no. 1190034, and GENCI French national computer center, Grant a0090807367.This research has been performed as part of the Chilean-French International Associated Laboratory for ?Multifunctional Molecules and Materials? (LIA M3-CNRS N?1207). Financial support from the Fondo Nacional de Desarrollo Cient?fico y Tecnol?gico [FONDECYT (Chile), grant no. 1190034 (D.C. and C.M.)], the Vicerrector?a de Investigaci?n y Estudios Avanzados, Pontificia Universidad Cat?lica de Valpara?so, Chile (D.C. and C.M.), the CNRS and the Universit? de Rennes 1 are gratefully acknowledged. The GENCI French national computer center is acknowledged for computational resources (Grant a0090807367). N.N. thanks also the CONICYT (Chile) and BECAS-CHILE for support of a graduate and Joint Supervision Scholarship (PUCV/UR1).
Funding Information:
Acknowledgments: This research has been performed as part of the Chilean-French International Associated Laboratory for “Multifunctional Molecules and Materials“ (LIA M3-CNRS N◦1207). Financial support from the Fondo Nacional de Desarrollo Científico y Tecnológico [FONDECYT (Chile), grant no. 1190034 (D.C. and C.M.)], the Vicerrectoría de Investigación y Estudios Avanzados, Pontificia Universidad Católica de Valparaíso, Chile (D.C. and C.M.), the CNRS and the Université de Rennes 1 are gratefully acknowledged. The GENCI French national computer center is acknowledged for computational resources (Grant a0090807367). N.N. thanks also the CONICYT (Chile) and BECAS-CHILE for support of a graduate and Joint Supervision Scholarship (PUCV/UR1).
Publisher Copyright:
© 2021 by the authors. Licensee MDPI, Basel, Switzerland.
PY - 2021/9
Y1 - 2021/9
N2 - We have recently reported a series of neutral square planar tridentate Schiff base (L) complexes of the general formula [(L)M(py)], showing relatively high first-order hyperpolarizabilities and NLO redox switching behavior. In the present study, new members of this family of compounds have been prepared with the objective to investigate their potential as building blocks in the on-demand construction of D-π-A push–pull systems. Namely, ternary nickel(II) building blocks of general formula [(LA/D)Ni(4-pyX)] (4–7), where LA/D stands for an electron accepting or donating dianionic O,N,O-tridentate Schiff base ligand resulting from the monocondensation of 2-aminophenol or its 4-substituted nitro derivative and β-diketones R-C(=O)CH2C(=O)CH3 (R = methyl, anisyl, ferrocenyl), and 4-pyX is 4-iodopyridine or 4-ethynylpyridine, were synthesized and isolated in 60–78% yields. Unexpectedly, the Sonogashira cross-coupling reaction between the 4-iodopyridine derivative 6 and 4-ethynylpyridine led to the formation of the bis(4-pyridyl) acetylene bridged centrosymmetric dimer [{(LD)Ni}2 (µ2-py-C≡C-py)] (8). Complexes 4–8 were characterized by elemental analysis, FT-IR and NMR spectroscopy, single crystal X-ray diffraction and computational methods. In each compound, the four-coordinate Ni(II) metal ion adopts a square planar geometry with two nitrogen and two oxygen atoms as donors occupying trans positions. In 8, the Ni … Ni separation is of 13.62(14) Å. Experimental results were proved and explained theoretically exploiting Density Functional Theory calculations.
AB - We have recently reported a series of neutral square planar tridentate Schiff base (L) complexes of the general formula [(L)M(py)], showing relatively high first-order hyperpolarizabilities and NLO redox switching behavior. In the present study, new members of this family of compounds have been prepared with the objective to investigate their potential as building blocks in the on-demand construction of D-π-A push–pull systems. Namely, ternary nickel(II) building blocks of general formula [(LA/D)Ni(4-pyX)] (4–7), where LA/D stands for an electron accepting or donating dianionic O,N,O-tridentate Schiff base ligand resulting from the monocondensation of 2-aminophenol or its 4-substituted nitro derivative and β-diketones R-C(=O)CH2C(=O)CH3 (R = methyl, anisyl, ferrocenyl), and 4-pyX is 4-iodopyridine or 4-ethynylpyridine, were synthesized and isolated in 60–78% yields. Unexpectedly, the Sonogashira cross-coupling reaction between the 4-iodopyridine derivative 6 and 4-ethynylpyridine led to the formation of the bis(4-pyridyl) acetylene bridged centrosymmetric dimer [{(LD)Ni}2 (µ2-py-C≡C-py)] (8). Complexes 4–8 were characterized by elemental analysis, FT-IR and NMR spectroscopy, single crystal X-ray diffraction and computational methods. In each compound, the four-coordinate Ni(II) metal ion adopts a square planar geometry with two nitrogen and two oxygen atoms as donors occupying trans positions. In 8, the Ni … Ni separation is of 13.62(14) Å. Experimental results were proved and explained theoretically exploiting Density Functional Theory calculations.
KW - DFT calculations
KW - Nickel
KW - Schiff base complexes
KW - Sonogashira cross coupling
KW - X-ray crystal structure
UR - http://www.scopus.com/inward/record.url?scp=85114352964&partnerID=8YFLogxK
U2 - 10.3390/molecules26175316
DO - 10.3390/molecules26175316
M3 - Article
AN - SCOPUS:85114352964
VL - 26
JO - Molecules
JF - Molecules
SN - 1420-3049
IS - 17
M1 - 5316
ER -