Luminescent Pt(II) Complexes Containing (1-Aza-15-crown-5)dithiocarbamate and (1-Aza-18-crown-6)dithiocarbamate: Mechanochromic and Solvent-Induced Luminescence

Biing-Chiau Tzeng; Chi-Chung Liao; Peng-Yuan Jung; Si-Ying Chen; Bing-Jian Sun; Wei-Chung Cheng; Agnes H H Chang; Gene-Hsiang Lee

doi:10.1021/acs.inorgchem.2c03726

Luminescent Pt(II) Complexes Containing (1-Aza-15-crown-5)dithiocarbamate and (1-Aza-18-crown-6)dithiocarbamate: Mechanochromic and Solvent-Induced Luminescence

Inorg Chem. 2023 Jan 16;62(2):916-929. doi: 10.1021/acs.inorgchem.2c03726. Epub 2022 Dec 30.

Authors

Biing-Chiau Tzeng¹, Chi-Chung Liao¹, Peng-Yuan Jung¹, Si-Ying Chen², Bing-Jian Sun², Wei-Chung Cheng¹, Agnes H H Chang², Gene-Hsiang Lee³

Affiliations

¹ Department of Chemistry and Biochemistry, National Chung Cheng University, 168 University Road, Min-Hsiung, Chiayi 62102, Taiwan.
² Department of Chemistry, National Dong Hwa University, 1, Sec. 2, Da Hsueh Road, Shoufeng, Hualien 97401, Taiwan.
³ Department of Chemistry, National Taiwan University, 1, Sec. 4, Roosevelt Road, Taipei 10617, Taiwan.

PMID: 36584668
DOI: 10.1021/acs.inorgchem.2c03726

Abstract

The strong tendency to stack in the solid state and rich luminescence for the Pt(II) complexes makes them potential candidates as new mechanochromic materials and sensing applications. Six mononuclear complexes [Pt(ppy)(O₄NCS₂)] (1), [Pt(bpy)(O₄NCS₂)]ClO₄ (2), [Pt(ppy)(O₅NCS₂)] (3), [Pt(phen)(O₄NCS₂)]ClO₄·CH₃OH (5a), [Pt(phen)(O₄NCS₂)]ClO₄ (5b), and [Pt(phen)(O₅NCS₂)]ClO₄ (6a), one dinuclear complex [Pt₂(phen)₂(NaO₅NCS₂)₂(ClO₄)₃]ClO₄ (6b), and one one-dimensional (1-D) coordination polymer {[Pt₂(bpy)₂(NaO₅NCS₂)₂(ClO₄)₂](ClO₄)₂}_n (4) were synthesized by reacting [Pt(ppy)Cl]₂, Pt(bpy)Cl₂, and Pt(phen)Cl₂ (ppy = 2-phenylpyridine, bpy = 2,2'-bipyridine, and phen = 1,10-phenanthroline) with (1-aza-15-crown-5)dithiocarbamate (O₄NCS₂) or (1-aza-18-crown-6)dithiocarbamate (O₅NCS₂), respectively, which have been isolated and structurally characterized by X-ray diffraction. Neutral complexes 1 and 3 contain no intermolecular Pt(II)···Pt(II) contact, whereas cationic complexes 2, 5a, 5b, and 6a with ClO₄^- as counteranions show alternative intermolecular Pt(II)···Pt(II) contacts of 3.535/4.091, 3.480/5.001, 3.527/4.571, and 3.446/4.987 Å in the solid state, respectively. Interestingly, complex 4 forms a 1-D coordination polymer through coordination between the encapsulated Na⁺ ions inside the azacrown ether rings of O₅NCS₂ and ClO₄^- anions with respective intra- and intermolecular Pt(II)···Pt(II) contacts of 3.402 and 3.847 Å in crystal lattices, whereas a dinuclear complex 6b was surprisingly formed and also connected by the encapsulated Na⁺ ions and ClO₄^- anions with alternative intra- and intermolecular Pt(II)···Pt(II) contacts of 3.650 and 3.677/4.4.372 Å, respectively. Upon excitation, complexes 1 and 3 showed similar vibronic luminescence at 507, 534, and 502, 532 nm, respectively, and the other complexes 2 and 4-6 showed broad luminescence with maxima at 537-567 nm. The B3LYP/LanL2DZ calculation was carried out and used to clarify their excited-state properties. In addition, the powder samples for complexes 1-4 almost showed no energy shift for the luminescence and significantly those of complexes 5-6 exhibited the mechanochromic luminescence upon grinding. It is noted that complexes 5a and 6a only showed minor red shifts (i.e., from 544 to 556 nm for complex 5a and from 551 to 565 nm for complex 6a), whereas complex 6b exhibited a remarkable red shift from 558 to 603 nm upon grinding. Besides, their luminescence reversibility was also examined toward various solvents.