posted on 2023-12-18, 20:07authored byKatarzyna Jędrzejowska, Jedrzej Kobylarczyk, Dominika Tabor, Monika Srebro-Hooper, Kunal Kumar, Guanping Li, Olaf Stefanczyk, Tadeusz M. Muzioł, Katarzyna Dziedzic-Kocurek, Shin-ichi Ohkoshi, Robert Podgajny
Optically active
functional noncentrosymmetric architectures might
be achieved through the combination of molecules with inscribed optical
responses and species of dedicated tectonic character. Herein, we
present the new series of noncentrosymmetric cocrystal salt solvates
(PPh4)3[M(CN)6](L)n·msolv (M = Cr(III), Fe(III), Co(III);
L = polyresorcinol coformers, multiple hydrogen bond donors: 3,3′,5,5′-tetrahydroxy-1,19-biphenyl,
DiR, n = 2, or 5′-(3,5-dihydroxyphenyl)-3,3″,5,5″-tetrahydroxy-1,19:3′,1″-terphenyl,
TriRB, n = 1) denoted as MDiR and MTriRB, respectively. The hydrogen-bonded subnetworks {[M(CN)6]3–;Ln}∞ of dmp, neb, or dia topology are formed through structural matching between
building blocks within supramolecular cis-bis(chelate)-like
{[M(CN)6]3–;(H2L)2(HL)2}
or tris(chelate)-like {[M(CN)6]3–;(H2L)3} fragments. The quantum-chemical
analysis demonstrates the mixed electrostatic and covalent character
of these interactions, with their strength clearly enhanced due to
the negative charge of the hydrogen bond acceptor metal complex. The
corresponding interaction energy is also dependent on the geometry
of the contact and size matching of its components, rotational degree
of freedom and extent of the π-electron system of the coformer,
and overall fit to the molecular surroundings. Symmetry of the crystal
lattices is correlated with the local symmetry of coformers and {complex;(coformer)n} hydrogen-bonded motifs characterized by
the absence of the inversion center and mirror plane. All compounds
reveal second-harmonic generation activity and photoluminescence diversified
by individual UV–vis spectral characteristics of the components,
and interesting low-frequency Raman scattering spectra within the
subterahertz spectroscopic domain. Vibrational (infrared/Raman), UV–vis
electronic absorption (experimental and calculated), and 57Fe Mössbauer spectra together with electrospray ionization
mass spectrometry (ESI-MS) data are provided for the complete description
of our systems.