Structural Elucidation of Selective Solvatochromism in a Responsive‐at‐Metal Cyclometalated Platinum(II) Complex

Soto, Miguel A.; Carta, Veronica; Andrews, Ryan J.; Chaudhry, Mohammad T.; MacLachlan, Mark J.

doi:10.1002/ange.202002646

Cited by 5 publications

(9 citation statements)

References 23 publications

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“…DFT/time-dependent (TD)-DFT calculations were carried out for monomeric species of 1a, 1b, and 3a in CH 2 Cl 2 (Tables S7−S9 and Figures S13−S16). In complexes 1, the low-energy feature is mainly assigned to a 1 IL/ 1 MLCT admixture with some 1 XLCT (X = Cl) character, whereas bis-isocyanide complex 3a has an important 1 IL character, with some ligand-to-ligand ( 1 LL′CT, C ∧ N → C�N) and ligand-to-metal 1 LMCT character. The red shift observed for the ppy-CHO complexes (b) in relation to the dfppy (a) can be related to the stabilization of the LUMO induced by the presence of the aldehyde moiety (−1.98 1a vs −2.43 eV 1b), whereas the HOMO remains similar (−6.16 1a vs −6.14 eV 1b), which reduces the HOMO−LUMO gap.…”

Section: ■ Crystallographic Studiesmentioning

confidence: 99%

“…Currently, there is a great deal of interest in producing chromic Pt II complexes, with changes in the color or luminescence upon the application of external stimuli. 1 Most of the studies focus on changes in luminescence using as external stimuli liquids, 2 vapors, 3 temperature, 3d,4 or mechanical grinding 5 of interest in memory, sensors, and optoelectronics. 6 Some excellent reviews about these topics have been published.…”

Section: ■ Introductionmentioning

confidence: 99%

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Multistimuli-Responsive Properties of Aggregated Isocyanide Cycloplatinated(II) Complexes

Martínez-Junquera

Lalinde

2022

Inorg. Chem.

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Here, we describe the neutral cyclometalated tert- butylisocyanide Pt II complexes, [Pt(C ∧ N)Cl(CNBu t )] 1 , the double salts [Pt(C ∧ N)(CNBu t ) 2 ][Pt(C ∧ N)Cl 2 ] 2 , and the cationic complexes [Pt(C ∧ N)(CNBu t ) 2 ]ClO 4 3 [C∧N = difluorophenylpyridine (dfppy, a ), 4-(2-pyridyl)benzaldehyde (ppy-CHO, b )]. A comparative study of the pseudopolymorphs 1a , 1a·CHCl 3 , 1b , 1b·0.5Toluene , 1b·0.5PhF , and 3a·0.25CH 2 Cl 2 reveals strong aggregation through Pt···Pt and/or π···π stacking interactions to give a variety of distinctive one-dimensional (1D) infinite chains, which modulate the photoluminescent properties. This intermolecular long-range aggregate formation is the main origin of the photoluminescent behavior of 1a and 1b complexes, which exhibit highly sensitive and reversible responses to multiple external stimuli including different volatile organic compounds (VOCs), solvents, temperatures, and pressures, with distinct color and phosphorescent color switching from green to red. Furthermore, complex 1b undergoes supramolecular self-assembly via Pt···Pt and/or π···π interactions into a polymer thin polystyrene (PS) film 10 wt % in response to toluene vapors, and 3a exhibits vapochromic and vapoluminescent behavior. Theoretical simulations on the dimer, trimer, and tetramer models of 1a and 1b have been carried out to get insight into the photophysical properties in the aggregated solid state.

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Section: ■ Crystallographic Studiesmentioning

confidence: 99%

Section: ■ Introductionmentioning

confidence: 99%

Multistimuli-Responsive Properties of Aggregated Isocyanide Cycloplatinated(II) Complexes

Martínez-Junquera

Lalinde

2022

Inorg. Chem.

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“…Compounds A, 1 B, 1 1-Pt II , 1 and tetraethylene glycol ditosylate 2 were synthesized according to previous methodologies. The collected spectroscopic data ( 1 H NMR and MS) matched well with those reported.…”

Section: Generalmentioning

confidence: 99%

“…All combined organic layers were dried (Na2SO4) and evaporated under vacuum to yield a dark yellow solid that was washed with MeCN (15 mL). 1 H NMR analysis (Figure S1a) of the crude material revealed full conversion of the ligand into 18C6-Pt II (23%) and 18C6-Pt IV (77%). Crystals of 18C6-Pt IV suitable for SCXRD analysis were obtained through slow vapor diffusion of hexanes into a solution of 18C6-Pt IV in DCM; the corresponding solid-state structure is shown in Figure S1b,c.…”

Section: S4mentioning

confidence: 99%

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

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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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Structural Elucidation of Selective Solvatochromism in a Responsive‐at‐Metal Cyclometalated Platinum(II) Complex

Cited by 5 publications

References 23 publications

Multistimuli-Responsive Properties of Aggregated Isocyanide Cycloplatinated(II) Complexes

Multistimuli-Responsive Properties of Aggregated Isocyanide Cycloplatinated(II) Complexes

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

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

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