Multiresponsive Cyclometalated Crown Ether Bearing a Platinum(II) Metal Center

Soto, Miguel A.; Carta, Veronica; Cano, Maria T.; Andrews, Ryan J.; Patrick, Brian O.; MacLachlan, Mark J.

doi:10.1021/acs.inorgchem.1c03178

Cited by 16 publications

(22 citation statements)

References 54 publications

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“…Pt(II) complexes with cyclometalated 2-arylpyridines and related terdentate and tetradentate ligands constitute one of the most intensively studied classes of organometallic compounds because of their useful photophysical and photochemical properties, which make them suitable for diverse light-based applications, , e.g., as phosphorescent dopants for organic light-emitting devices (OLEDs), ,− probes for bioimaging, − chemosensors, − or photoredox catalysts. − The development of new cyclometalated Pt(II) complexes critically depends on the availability of convenient synthetic methodologies. The cycloplatination of 2-arylpyridines and related C∧N ligands is commonly achieved under thermal conditions, most often by heating K 2 [PtCl 4 ] and the ligand in alcohol/water mixtures. − This method often presents disadvantages, such as partial decomposition to Pt(0).…”

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confidence: 99%

“…Pt(II) complexes with cyclometalated 2-arylpyridines and related terdentate and tetradentate ligands constitute one of the most intensively studied classes of organometallic compounds because of their useful photophysical and photochemical properties, which make them suitable for diverse light-based applications, 37 , 38 e.g., as phosphorescent dopants for organic light-emitting devices (OLEDs), 5 , 39 − 42 probes for bioimaging, 43 − 45 chemosensors, 46 − 49 or photoredox catalysts. 50 − 53 The development of new cyclometalated Pt(II) complexes critically depends on the availability of convenient synthetic methodologies.…”

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confidence: 99%

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Photochemically Induced Cyclometalations at Simple Platinum(II) Precursors

et al. 2023

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Photochemical cycloplatinations of 2-arylpyridines and related C∧N ligands, as well as terdentate heteroaromatic N∧N∧C, N∧C∧N, and N∧C∧C compounds, are demonstrated using (Bu4N)2[Pt2Cl6] or [PtCl2(NCPh)2] as precursors at room temperature. Mono- or bis-cyclometalated Pt(II) complexes with C∧N ligands are obtained depending on excitation wavelength and precursor. Monitoring experiments show that photoexcitation enables both the N-coordination and the subsequent C–H metalation. Photochemical synthetic protocols have been developed, which are advantageous with respect to the established thermal procedures and have allowed the synthesis of the first Pt(II) complexes with N∧C∧C ligands.

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confidence: 99%

“…Pt(II) complexes with cyclometalated 2-arylpyridines and related terdentate and tetradentate ligands constitute one of the most intensively studied classes of organometallic compounds because of their useful photophysical and photochemical properties, which make them suitable for diverse light-based applications, 37 , 38 e.g., as phosphorescent dopants for organic light-emitting devices (OLEDs), 5 , 39 − 42 probes for bioimaging, 43 − 45 chemosensors, 46 − 49 or photoredox catalysts. 50 − 53 The development of new cyclometalated Pt(II) complexes critically depends on the availability of convenient synthetic methodologies.…”

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confidence: 99%

Photochemically Induced Cyclometalations at Simple Platinum(II) Precursors

et al. 2023

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“…Phenylpyridine (phpy) derivatives are important in the synthesis of cyclometalated complexes (e.g., with Au III , Ir III , Pt II , and Pd II ) [22–25] . While bridged phpy ligands yield materials with intriguing stimuli‐responsiveness, [26–28] unbridged species unleash stereochemical diversity [29–32] . The 2‐phpy/Pt combination can yield up to five mononuclear complexes containing Pt II and Pt IV (Figure 2a) [33–36] .…”

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confidence: 99%

“…Clean transformation of complex 1 into 3 motivated us to investigate the processing of 2 . We and others have shown the reduction of Pt IV centers in cyclometalated complexes [26–28] . For 2 , we adapted a published method, [26] which gave exclusively one macrocycle, ring 4 (Scheme 1, Figure S6), in 26 % yield; we attribute the low isolated yield to the instability of the complex in the stationary phase (either SiO 2 or Al 2 O 3 ) used for purification.…”

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Cycling a Tether into Multiple Rings: Pt‐Bridged Macrocycles for Differentiated Guest Recognition, Pseudorotaxane Transformations, and Guest Capture and Release

et al. 2022

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Macrocycle engineering is a key topic in supramolecular chemistry. When synthesizing a ring, one can obtain either complex mixtures of macrocycles of different sizes or a single ring if a template is utilized. Here, we unite these approaches along with postsynthetic modifications to transform a single tether into multiple rings-up to five per tether. The macrocycles contain two bridged phenylpyridine ligands that are connected through a Pt atom, which defines the rings' shape, size, and host activity. All rings undergo redox reactions (between Pt II and Pt IV ) that allow for large conformational changes. Their reactivity, together with their host performance, is a convenient way to control the capture and release of guests, to mediate ring transformations, and to control pseudorotaxane-to-pseudorotaxane conversions. This novel approach could serve to assemble other libraries of small ring molecules, create cyclic polymers bridged by responsive-at-metal nodes, and produce processable mechanically interlocked molecules. Since Pedersen's seminal work on crown ethers, [1,2] the synthesis of macrocycles has been central to supramolecular chemistry. [3] The library of known ring molecules is vast, encompassing diverse compositions, geometries and sizes. [4][5][6][7][8][9] Macrocycles are being investigated for applications [10] such as sensing, [11] molecular delivery, [12] molecular machinery, [13] and more. [14] Macrocycle synthesis relies on one of the approaches depicted in Figure 1. The statistical approach proceeds under kinetic control and yields mixtures of linear and cyclic oligomers; [15] template-assisted syntheses operate under thermodynamic control, favoring one particular ring; [16] and post-synthetic modifications serve to alter preassembled rings. [17,18] Although these approaches are used disjointedly, we envisioned that by applying all three in tandem, a single precursor-the tether-could be transformed into multiple rings. Forming and isolating many macrocycles from one tether is not only economical but can also lead to rings with distinct cavity sizes, and hence differentiated host activity.Labile and inert metal-organic compounds have been crucial in recent developments of supramolecular chemistry. [19][20][21] Phenylpyridine (phpy) derivatives are important in the synthesis of cyclometalated complexes (e.g., with

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“…First, we synthesized the flytrap by chemical oxidation of 1 [32] (Scheme S1). A solution of complex 1 (5.…”

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Molecular Flytraps Held Together by Platinum–Platinum Intermetallic Bonds

et al. 2023

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Metal‐metal bonds have rarely been explored as active elements in supramolecular assemblies despite their unique potential to introduce responsive behavior. In this report, a dynamic molecular container composed of two cyclometalated Pt units is constructed using Pt−Pt bonds. This molecule—the flytrap—has a flexible jaw composed of two [18]crown‐6 ethers that can adapt their shape to bind large inorganic cations with sub‐micromolar affinity. Along with the spectroscopic and crystallographic characterization of the flytrap, we report its photochemical assembly, which allows the capture of ions and their transport from solution to the solid state. In addition, we have been able to recycle the flytrap to regenerate its starting material due to the reversible nature of the Pt−Pt bond. We believe that other molecular containers and materials for harvesting valuable substrates from solution could be assembled using the advances presented here.

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Multiresponsive Cyclometalated Crown Ether Bearing a Platinum(II) Metal Center

Cited by 16 publications

References 54 publications

Photochemically Induced Cyclometalations at Simple Platinum(II) Precursors

Photochemically Induced Cyclometalations at Simple Platinum(II) Precursors

Cycling a Tether into Multiple Rings: Pt‐Bridged Macrocycles for Differentiated Guest Recognition, Pseudorotaxane Transformations, and Guest Capture and Release

Molecular Flytraps Held Together by Platinum–Platinum Intermetallic Bonds

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