Designed materials offer noteworthy applications which are often architecture dependent. Despite knowing such a fact, one of the major challenges faced by the scientific community is to find ways to predict and, if possible, control the resultant architecture of a network. If such an exercise is fruitful, it creates enormous opportunities to synthesize exotic materials with tailor-made applications. Any network is composed of individual molecules and the transition from a single molecule to a network can be achieved through several routes taking advantage of synthetic chemistry. There exists a molecular building block at the heart of such a transition which mediates such a process from a single molecule to a network. Although a large number of building blocks have created assorted materials, utilization of a well-defined coordination complex as the building block (i.e., metalloligand) is unique for the construction of a designed architecture. A coordination complex as the building block offers structural rigidity that places the auxiliary functional groups to a pre-organized conformation. Such auxiliary functional groups could then coordinate a secondary metal ion or be involved in the self-assembly via weak interactions, such as hydrogen bonds. This review focuses on the recent progress achieved through assorted molecular building blocks towards generating ordered networks. Broadly, two classes of metalloligands will be discussed: those offering hydrogen bond sensitive functional groups and those tendering coordination bond responsive groups. Nevertheless, the result is the construction of networks of a highly-ordered nature in both cases. The present review is expected to provide new strategies for constructing functional materials through metalloligands for challenging and practical applications.

Molecularly designed architectures – the metalloligand way

Regulation of metal–metal interactions and chromic phenomena of multi-decker platinum complexes having π-systems

The half-lantern compound [{Pt(bzq)(μ-C7H4NS2-κN,S)}2]·Me2CO (1) was obtained by reaction of equimolar amounts of potassium 2-mercaptobenzothiazolate (KC7H4NS2) and [Pt(bzq)(NCMe)2]ClO4. The Pt(II)···Pt(II) separation in the neutral complex [{Pt(bzq)(μ-C7H4NS2-κN,S)}2] is 2.910 (2) A, this being among the shortest observed in half-lantern divalent platinum complexes. Within the complex, the benzo[h]quinoline (bzq) groups lie in close proximity with most C···C distances being between 3.3 and 3.7 A, which is indicative of significant π–π interactions. The reaction of 1 with halogens X2 (X2 = Cl2, Br2, or I2) proceeds with a two-electron oxidation to give the corresponding dihalodiplatinum(III) complexes [{Pt(bzq)(μ-C7H4NS2-κN,S)X}2] (X = Cl 2, Br 3, I 4). Their X-ray structures confirm the retention of the half-lantern structure and the coordination mode of the bzq and the bridging ligand μ-C7H4NS2-κN,S. The Pt–Pt distances (Pt–Pt = 2.6420(3) A 2, 2.6435(4) A 3, 2.6690(3) A 4) are shorter than that in 1 bec...

Highly luminescent half-lantern cyclometalated platinum(II) complex: Synthesis, structure, luminescence studies, and reactivity

Dinuclear Pt(III) complexes were commonly reported to have short-lived lowest-lying triplet states, resulting in extremely weak or no photoluminescence. To overcome this obstacle, a new series of dinuclear Pt(III) complexes, named Pt2a-Pt2c, were strategically designed and synthesized using donor (D)-acceptor (A)-type oxadiazole-thiol chelates as bridging ligands. These dinuclear Pt(III) complexes possess a d7-d7 electronic configuration and exhibit intense phosphorescence under ambient conditions. Among them, Pt2a exhibits orange phosphorescence maximized at 618 nm in degassed dichloromethane solution (Φp ≈ 8.2%, τp ≈ 0.10 μs) and near-infrared (NIR) emission at 749 nm (Φp ≈ 10.1% τp ≈ 0.66 μs) in the crystalline powder and at 704 nm (Φp ≈ 33.1%, τp ≈ 0.34 μs) in the spin-coated neat film. An emission blue-shifted by more than 3343 cm-1 is observed under mechanically ground crystalline Pt2a, affirming intermolecular interactions in the solid states. Time-dependent density functional theory (TD-DFT) discloses the lowest-lying electronic transition of Pt2a-Pt2c complexes to be a bridging ligand-metal-metal charge transfer (LMMCT) transition. The long-lived triplet states of these dinuclear platinum(III) complexes may find potential use in lighting. Employing Pt2a as an emitter, high-performance organic light-emitting diodes (OLEDs) were fabricated with NIR emission at 716 nm (η = 5.1%), red emission at 614 nm (η = 8.7%), and white-light emission (η = 11.6%) in nondoped, doped (in mCP), and hybrid (in CzACSF) devices, respectively.

Highly Emissive Dinuclear Platinum(III) Complexes.

https://onlinelibrary.wiley.com/doi/pdf/10.1002/9781119007166.ch1

Archetypal Iridium(III) Compounds for Optoelectronic and Photonic Applications

Structures and Luminescence Properties of Cyclometalated Dinuclear Platinum(II) Complexes Bridged by Pyridinethiolate Ions

Emission from a cationic cyclometalated iridium(III) complex, Δ- or Λ-[Ir(ppy)2(dmbpy)]+ (Hppy: 2-phenylpyridine and dmbpy: 4,4′-dimethyl-2,2′-bipyridine), adsorbed on a colloidal saponite clay was...

Enantioselective Sensing by Luminescence from Cyclometalated Iridium(III) Complexes Adsorbed on a Colloidal Saponite Clay

We synthesized a thiosemicarbazone-functionalized flavin (Fl-(H)TSC: 2-[2-(3,4-dihydro-7,8-dimethyl-2,4-dioxobenzo[g]pteridin-10(2H)-yl)ethylidene]-hydrazinecarbothioamide) and its Pt(II) complex [Pt(Fl-TSC)2], and characterized it using X-ray diffraction, UV–visible absorption and luminescence spectroscopy. X-ray structural analysis for [Pt(Fl-TSC)2] revealed that the structure of the isoalloxazine part was almost the same as that in lumiflavin (7,8,10-trimethylisoalloxazine), and the thiosemicarbazone moiety acted as a bidentate ligand to form a PtS2N2 planar conformation. UV–visible absorption and luminescence spectra of these compounds were very similar to those of riboflavin, but the emission intensity and the lifetime decreased considerably. Theoretical calculations suggested that the charge-separated state (Fl˙−-TSC˙+) contributed to the faster quenching from the 1π–π* emission state.

/pdf/synthesis-structure-and-photophysical-properties-of-a-flavin-p2ymppmg0m.pdf

Synthesis, structure and photophysical properties of a flavin-based platinum(II) complex.

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Structures and Luminescence Properties of Cyclometalated Dinuclear Platinum(II) Complexes Bridged by Pyridinethiolate Ions

Enantioselective Sensing by Luminescence from Cyclometalated Iridium(III) Complexes Adsorbed on a Colloidal Saponite Clay

Synthesis, structure and photophysical properties of a flavin-based platinum(II) complex.