Recent advances in supramolecular self‐assembly and biological applications of luminescent alkynylplatinum(II) polypyridine complexes

Abstract

Among various transition metal complexes, platinum(II) complexes are among one of the most extensively explored classes of metal complexes for supramolecular assembly, as their square-planar molecular geometry allows axial interactions between adjacent complex molecules and access to the formation of supramolecular assemblies with the aid of noncovalent Pt(II)Á Á ÁPt(II) interactions. In the presence of external stimuli, alkynylplatinum(II) polypyridine complexes can selfassemble with alterations in their spectroscopic and luminescence properties. In light of their inherent advantages, including low-energy photoexcitation, red to near-infrared emission, large Stokes shifts, long phosphorescence lifetimes and high photostability, successful applications of alkynylplatinum(II) polypyridine complexes in the detection of biological analytes have been made possible. In this account, presented in part of the FACS Foundation Lecture, we introduce the basic concepts and our recent advances in the development of detection assays for various biomolecules based on luminescent alkynylplatinum(II) polypyridine complexes with selected examples.

Controlled Supramolecular Assembly of Gold (III) Amphiphiles in Aqueous Media

“…1 H NMR (400 MHz, CDCl 3 ) δ 8.64 (d, J = 4.7 Hz, 1H), 7.96-7.89 (m, 2H), 7.75-7.63 (m, 2H), 7.20-7.12 (m, 1H), 7.03-6.94 (m, 2H), 4.01 (t, J = 6.5 Hz, 2H), 3.63 (t, J = 6.7 Hz, 2H), 1.86-1.74 (m, 2H), 1.61-1.51 (m, 2H), 1.51-1.42 (m, 2H), 1.40-1.29 (m, 8H). 13 Compound 2: Compound 2 was synthesized according to a published method. [43] Compound 1 (673 mg, 2.15 mmol) and Hg-(OAc) 2 (754 mg, 2.37 mmol) were suspended in ethanol (EtOH, 10 mL) and refluxed for 48 h. Then, a methanol solution (MeOH, 5 mL) of LiCl (201 mg, 4.73 mmol) was added to the reaction mixture.…”

“…Amphiphile is one of the key candidates in the design of synthetic organic molecules with high functional tunability and aqueous solubility, as amphiphilic structures interact differently with solvent/water [4,11] . Compared with the extensively investigated supramolecular assemblies and co‐assemblies of organic amphiphiles, [5] metal‐ligand amphiphiles serve as a promising alternative for their structural diversity and versatility of ligand modifications via simpler synthetic strategies [12–16] . The tunability of metal‐ligand amphiphile design allows a delicate control in structure and intermolecular interactions with various noncovalent interactions [12,16] …”

“…[4,11] Compared with the extensively investigated supramolecular assemblies and co-assemblies of organic amphiphiles, [5] metal-ligand amphiphiles serve as a promising alternative for their structural diversity and versatility of ligand modifications via simpler synthetic strategies. [12][13][14][15][16] The tunability of metal-ligand amphiphile design allows a delicate control in structure and intermolecular interactions with various noncovalent interactions. [12,16] Gold (I) and gold (III) complexes, known for their wide range of applications in catalysis, [17][18][19] optoelectronic materials [20,21] and bioconjugation methodologies, [22][23][24] have been extensively developed due to their unique luminescence properties and aqueous stability.…”

“…13 C NMR (101 MHz, CDCl 3 ) 160.2, 155.4, 147.8, 138.1, 133.9, 127.8, 123.6, 122.6, 119.6, 114.8, 68.2, 34.1, 32.8, 29.4, 29.3, 29.2, 28.7, 28.2, 26.0. HR-MS (ESI +) calculated for C 20 H 25 BrClHgNO [M + H] + 612.0570 found 612.0558.…”

“…13 C NMR (101 MHz, CD 3 OD) δ 164.8, 160.3, 153.2, 147.6, 143.2, 134.3, 127.4, 123.0, 120.8, 116.0, 114.9, 68.2, 66.5, 52.1, 28.9, 28.7, 28.7, 28.5, 25.9, 25.5, 22.6. HR-MS (ESI +) calculated for C 23 H 34 AuCl 2 N 2 O [MÀ Br] + 621.1714 found 621.1710.…”