Luminescent cyclometalated platinum(ii) complexes with acyclic diaminocarbene ligands: structural, photophysical and biological properties

被引：30

作者：

Martinez-Junquera, Monica ^{[1
]}

Lalinde, Elena ^{[1
]}

Moreno, M. Teresa ^{[1
]}

Alfaro-Arnedo, Elvira ^{[2
]}

Lopez, Iciar P. ^{[2
]}

Larrayoz, Ignacio M. ^{[3
]}

Pichel, Jose G. ^{[2
,4
]}

机构：

[1] Univ La Rioja, Ctr Sintesis Quim La Rioja CISQ, Dept Quim, Logrono 26006, Spain

[2] Fdn Rioja Salud, Lung Canc & Resp Dis Unit CIBIR, Logrono 26006, Spain

[3] Fdn Rioja Salud, Biomarkers & Mol Signaling Unit CIBIR, Logrono 26006, Spain

[4] ISCIII, Biomed Res Networking Ctr Resp Dis CIBERES, Madrid, Spain

来源：

DALTON TRANSACTIONS | 2021年 / 50卷 / 13期

关键词：

CARBENE COMPLEXES;

D O I：

10.1039/d1dt00480h

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

Four new cyclometalated Pt(ii) complexes bearing acyclic diaminocarbene (ADC) ligands, [Pt(C<^>N)Cl{C(NHXyl)(NHR)}] [C<^>N = 2,6-difluorophenylpyridine (dfppy), phenylquinoline (pq); R = Pr 3a, 4a, CH2Ph 3b, 4b], were prepared by the nucleophilic attack on the isocyanide [Pt(C<^>N)Cl(CNXyl)] (C<^>N = dfppy 1, pq 2) by the corresponding amine RNH2 (R = Pr, CH2Ph). Complexes 3 show in their H-1 NMR spectra in CDCl3 a notable concentration dependence, with a clear variation of the delta(H) (NHXyl) signal, suggesting an assembling process implying donor-acceptor NHXylMIDLINE HORIZONTAL ELLIPSISCl bonding, also supported by 1D-PGSE (Pulse Field Gradient Spin Echo) and 2D-DOSY (Diffusion Ordered Spectroscopy) NMR experiments in solution and X-ray diffraction studies. The intermolecular interactions in compounds 3a and 3b were studied by using Hirshfeld surface analysis and Non-Covalent Interaction (NCI) methods on their X-ray structures. Their photophysical properties were investigated by absorption and emission spectroscopies and also by TD-DFT calculations performed on 3a and 4b. These complexes show green (3) or orange (4) phosphorescence, attributed to a mixed (IL)-I-3/(MLCT)-M-3 excited state. The carbene ligand does not affect the emission maxima but it produces an increase of the quantum yields in relation to the isocyanide in the precursors. In fluid solutions, the emission is not concentration-dependent, but the complexes may show aggregation induced emission as detailed for complexes 3a and 4a. In addition, cytotoxicity studies in the human cell lines A549 (lung carcinoma) and HeLa (cervix carcinoma) showed good activity for these complexes and 3a, 3b and 4a exhibit a strong effect on DNA electrophoretic mobility. To the best of our knowledge, compounds 3 and 4 represent the first examples of cycloplatinated complexes bearing acyclic diamino carbenes with antiproliferative properties.

引用

页码：4539 / 4554

页数：16