TY - JOUR
T1 - Tuning the Structure and Flexibility of Coordination Polymers via Solvent Control of Tritopic Triazine Conformation during Crystallization
AU - Portolés-Gil, Núria
AU - López-Periago, Ana M.
AU - Borrás, Alejandro
AU - Fraile, Julio
AU - Solano, Eduardo
AU - Vallcorba, Oriol
AU - Planas, José G.
AU - Ayllón, José A.
AU - Domingo, Concepción
N1 - Funding Information:
This work was financed by the Spanish National Plan of Research with project CTQ2017-83632. C.D., J.G.P., A.B., N.P.-G., J.F., and A.M.L.-P. acknowledge the financial support from the Spanish MEC, through the Severo Ochoa Program for Centres of Excellence in R&D (SEV-2015-0496). This work (N.P.-G., A.B., and J.F.) has been done in the framework of the doctoral program “Chemistry” of the Universitat Autònoma de Barcelona. A.M.L.-P. acknowledges the RyC-2012-11588 contract. N.P.-G. and A.B. acknowledge FPI grants. ALBA synchrotron is acknowledged for the provision of beam time.
Publisher Copyright:
© 2020 American Chemical Society.
Copyright:
Copyright 2020 Elsevier B.V., All rights reserved.
PY - 2020/5/6
Y1 - 2020/5/6
N2 - Soft crystallization routes for the controlled growth of one- and two-dimensional Cu(II)-coordination polymers of the type [(Cu(hfa)2)x(3-tpt)]n (hfa = hexafluoroacetylacetonate, 3-tpt = 2,4,6-tris(3-pyridyl)-1,3,5-triazine) are described. Three volatile solvents with different protic/aprotic characteristics were chosen as the reaction media, e.g., supercritical CO2, chloroform, and ethanol. Five (1-5) new compounds were crystallized, with different structures and Cu(II)/3-tpt ratios. The structures of 3-tpt and five new coordination polymers were elucidated by single-crystal synchrotron X-ray diffraction. A description of the crystallization pathways followed for the synthesis of the individual compounds is given based on the protic or aprotic character of the used solvents and reagents' solubility constraints. The main novelty of the work relies in establishing the foundations of 3-tpt isomeric control during crystallization through solvent selection. From the five precipitated new compounds, 3 displays a significant framework flexibility, associated with N2 adsorption at low temperature, presenting a stepwise adsorption isotherm. The N2 adsorption process was followed by in situ synchrotron X-ray powder diffraction.
AB - Soft crystallization routes for the controlled growth of one- and two-dimensional Cu(II)-coordination polymers of the type [(Cu(hfa)2)x(3-tpt)]n (hfa = hexafluoroacetylacetonate, 3-tpt = 2,4,6-tris(3-pyridyl)-1,3,5-triazine) are described. Three volatile solvents with different protic/aprotic characteristics were chosen as the reaction media, e.g., supercritical CO2, chloroform, and ethanol. Five (1-5) new compounds were crystallized, with different structures and Cu(II)/3-tpt ratios. The structures of 3-tpt and five new coordination polymers were elucidated by single-crystal synchrotron X-ray diffraction. A description of the crystallization pathways followed for the synthesis of the individual compounds is given based on the protic or aprotic character of the used solvents and reagents' solubility constraints. The main novelty of the work relies in establishing the foundations of 3-tpt isomeric control during crystallization through solvent selection. From the five precipitated new compounds, 3 displays a significant framework flexibility, associated with N2 adsorption at low temperature, presenting a stepwise adsorption isotherm. The N2 adsorption process was followed by in situ synchrotron X-ray powder diffraction.
UR - http://www.scopus.com/inward/record.url?scp=85084701621&partnerID=8YFLogxK
U2 - 10.1021/acs.cgd.0c00088
DO - 10.1021/acs.cgd.0c00088
M3 - Article
VL - 20
SP - 3304
EP - 3315
JO - Crystal Growth and Design
JF - Crystal Growth and Design
SN - 1528-7483
IS - 5
ER -