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Heteroleptic mer-[Cr(N^∩N^∩N)(CN)₃] complexes: synthetic challenge, structural characterization and photophysical properties.

ABSTRACT: The substitution of three water molecules around trivalent chromium in CrBr₃·6H₂O with the tridentate 2,2':6',2''-terpyridine (tpy), N,N'-dimethyl-N,N'-di(pyridine-2-yl)pyridine-2,6-diamine (ddpd) or 2,6-di(quinolin-8-yl)pyridine (dqp) ligands gives the heteroleptic mer-[Cr(L)Br₃] complexes. Stepwise treatments with Ag(CF₃SO₃) and KCN under microwave irradiations provide mer-[Cr(L)(CN)₃] in moderate yields. According to their X-ray crystal structures, the associated six-coordinate meridional [CrN₃C₃] chromophores increasingly deviate from a pseudo-octahedral arrangement according to L = ddpd ≈ dpq ≪ tpy; a trend in line with the replacement of six-membered with five-membered chelate rings around Cr^III. Room-temperature ligand-centered UV-excitation at 18 170 cm^-1 (λ_exc = 350 nm), followed by energy transfer and intersystem crossing eventually yield microsecond metal-centered Cr(²E → ⁴A₂) phosphorescence in the red to near infrared domain 13 150-12 650 cm^-1 (760 ≤ λ_em ≤ 790 nm). Decreasing the temperature to liquid nitrogen (77 K) extends the emission lifetimes to reach the millisecond regime with a record of 4.02 ms for mer-[Cr(dqp)(CN)₃] in frozen acetonitrile.

SUBMITTER: Chong J

PROVIDER: S-EPMC8922558 | biostudies-literature | 2022 Mar

REPOSITORIES: biostudies-literature

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Heteroleptic mer-[Cr(N∩N∩N)(CN)3] complexes: synthetic challenge, structural characterization and photophysical properties.

Chong Julien J Besnard Céline C Cruz Carlos M CM Piguet Claude C Jiménez Juan-Ramón JR

Dalton transactions (Cambridge, England : 2003) 20220315 11

The substitution of three water molecules around trivalent chromium in CrBr3·6H2O with the tridentate 2,2':6',2''-terpyridine (tpy), N,N'-dimethyl-N,N'-di(pyridine-2-yl)pyridine-2,6-diamine (ddpd) or 2,6-di(quinolin-8-yl)pyridine (dqp) ligands gives the heteroleptic mer-[Cr(L)Br3] complexes. Stepwise treatments with Ag(CF3SO3) and KCN under microwave irradiations provide mer-[Cr(L)(CN)3] i ...[more]

PMID: 35195140

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Project description:Studies on molecular co-crystal type materials are important in the design and preparation of easy-to-absorb drugs, non-centrosymmetric, and chiral crystals for optical performance, liquid crystals, or plastic phases. From a fundamental point of view, such studies also provide useful information on various supramolecular synthons and molecular ordering, including metric parameters, molecular matching, energetical hierarchy, and combinatorial potential, appealing to the rational design of functional materials through structure-properties-application schemes. Co-crystal salts involving anionic d-metallate coordination complexes are moderately explored (compared to the generality of co-crystals), and in this context, we present a new series of isomorphous co-crystalline salts (PPh4)3[M(CN)6](H3PG)2·2MeCN (M = Cr, 1; Fe, 2; Co 3; H3PG = phloroglucinol, 1,3,5-trihydroxobenzene). In this study, 1-3 were characterized experimentally using SC XRD, Hirshfeld analysis, ESI-MS spectrometry, vibrational IR and Raman, 57Fe Mössbauer, electronic absorption UV-Vis-NIR, and photoluminescence spectroscopies, and theoretically with density functional theory calculations. The two-dimensional square grid-like hydrogen-bond {[M(CN)6]3-;(H3PG)2}∞ network features original {[M(CN)6]3-;(H3PG)4} supramolecular cis-bis(chelate) motifs involving: (i) two double cyclic hydrogen bond synthons M(-CN⋅⋅⋅HO-)2Ar, {[M(CN)6]3-;H2PGH}, between cis-oriented cyanido ligands of [M(CN)6]3- and resorcinol-like face of H3PG, and (ii) two single hydrogen bonds M-CN⋅⋅⋅HO-Ar, {[M(CN)6]3-;HPGH2}, involving the remaining two cyanide ligands. The occurrence of the above tectonic motif is discussed with regard to the relevant data existing in the CCDC database, including the multisite H-bond binding of [M(CN)6]3- by organic species, mononuclear coordination complexes, and polynuclear complexes. The physicochemical and computational characterization discloses notable spectral modifications under the regime of an extended hydrogen bond network.

Dataset Information

Heteroleptic mer-[Cr(N^∩N^∩N)(CN)₃] complexes: synthetic challenge, structural characterization and photophysical properties.

Publications

Heteroleptic <i>mer</i>-[Cr(N<sup>∩</sup>N<sup>∩</sup>N)(CN)<sub>3</sub>] complexes: synthetic challenge, structural characterization and photophysical properties.

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