Mechanical vs Electronic Strain: Oval-Shaped Alkynyl-Pt(II)-Phosphine Macrocycles

Plutnar, Jan; Givelet, Cécile; Lemouchi, Cyprien; Dytrtová, Jana Jaklová; Cı́sařová, Ivana; Teat, Simon J.; Michl, Josef

doi:10.1021/acs.organomet.9b00633

Cited by 6 publications

(8 citation statements)

References 42 publications

(107 reference statements)

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“…Experimental evidence shows that the most stable isomer of macrocycle of 1 , the all-trans isomer 1t 4 , is formed while 2 forms no cycle but linear all-trans oligomers instead . Geometry optimizations of linear tetramers (macrocycles opened at a Pt–C or Pt–N bond) of 1 and 2 could not be converged to determine the energy difference between the macrocycle and linear tetramer; however, as a proxy, the sum of the mechanical strains in the four fragments of a macrocycle from Table can serve as a good approximation in the case of macrocycle 1 and less so for 2 on the basis of their errors.…”

Section: Resultsmentioning

confidence: 99%

“…It thus seems unlikely that the linear tetramers, once formed, would ever cyclize, especially the cationic one. The fact that the formation of 1t 4 is actually observed suggests that the macrocyclization by self-assembly occurs early in the process, before the linear tetramer is formed, as proposed in the mechanism outlined in the earlier experimental paper . The fact that the even much more endothermic 2 is not formed at all is understandable.…”

Section: Discussionmentioning

confidence: 99%

“…With considerable encouragement from the presently reported calculations, the macrocycle containing four p,p′-bis(ethynyl)biphenyl rods has been more recently recognized by detailed analysis of NMR spectra to actually have a trans configuration at each Pt atom and to possess strongly bent triple bonds, which give it a surprising oval shape. 14 At the same time, the products containing two p,p′bis(ethynyl)biphenyl rods and two bis(4-pyridyl)ethyne (or bis(4-pyridyl)butadiyne) rods were shown not to be macrocycles but rather a mixture of linear oligomers.…”

Section: ■ Introductionmentioning

confidence: 99%

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Mechanical vs Electronic Strain: Calculated Configurations of Alkynyl-Pt(II)-Phosphine Macrocycles

Buchanan

Michl

2020

Organometallics

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Optimized geometries of macrocycles composed of four Pt(PR 3 ) 2 linkers and four rods terminated with ethynyl or pyridyl moieties have been calculated at the PBE0/Def2-TZVPP//PBE0/Def2-SVP level of density functional theory for all combinations of cis and trans configurations at the Pt centers. For uncharged complexes with four p,p′-bis(ethynyl)biphenyl rods and neutral Pt centers, the energy of the planar oval-shaped all-trans isomer lies 17 kcal/mol below that of the puckered square-shaped all-cis isomer. In this case, the electronic strain associated with the cis arrangement at the Pt atoms overrules the mechanical strain associated with the bending of triple bonds. For cationic complexes containing two bipyridyl and two p,p′bis(ethynyl)biphenyl rods, with a +1 charge on each Pt center, a puckered rectangular structure with all-cis Pt centers is found to be 38 kcal/mol lower in energy than the isomer with all four Pt centers trans. The results have been analyzed in terms of three additive factors, referred to as electronic, mechanical, and electrostatic strains.

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Section: Resultsmentioning

confidence: 99%

Section: Discussionmentioning

confidence: 99%

Section: ■ Introductionmentioning

confidence: 99%

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Mechanical vs Electronic Strain: Calculated Configurations of Alkynyl-Pt(II)-Phosphine Macrocycles

Buchanan

Michl

2020

Organometallics

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“…The rectangle corners are occupied with bidentate phosphine‐containing cis‐coordinated Pt(II)‐alkynes. [ 65 ]…”

Section: Platinum(ii)‐based Molecules: Self‐assembly With Donor Ligan...mentioning

confidence: 99%

Topical progress in medicinal applications of self‐assembled organoplatinum complexes using diverse Pt(II)‐ and N‐based tectons

Kumar

Jana

Bhowmick

et al. 2022

Applied Organom Chemis

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The last decade witnessed a flourishing advancement in the design and synthesis of discrete Pt‐based metallamacrocycles self‐assembled using coordination bonds. Such supramolecular entities were obtained using novel nitrogen‐based ligands and have wide and versatile applications such as chemical sensors, catalysts, theranostic agents, optical materials, drug delivery, and others. Herein, we present a concise review of recently reported metallacycles obtained using various N‐functionalized donor and Pt acceptor tectons of various shapes and sizes. While highlighting recent developments in the syntheses and characterization of such platinacycles, we lay special emphasis on their biological interactions and applications.

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“…Michl and co‐workers reported tetranuclear heteroleptic Pt(II) core‐based ionic rectangles ([ 8 a ] 4+ and [ 8 b ] 4+ ), a neutral rectangle [ 8 c ] and an ionic bicyclic cage [25] . The self‐assembly of these metallacycles were achieved using triptycene spacer‐based Pt(II) ditopic metalloligand acceptors with neutral/dianionic donors.…”

Section: Bicyclic Organic Spacer Based Ligands and Its Sccsmentioning

confidence: 99%

Emerging Spacers‐Based Ligands for Supramolecular Coordination Complexes

Mishra

Bhol

Kalimuthu

et al. 2021

The Chemical Record

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The design and self‐assembly of supramolecular coordination complexes (SCCs) i. e., discrete cyclic metalloarchitectures such as cycles, cages, mesocates, and helicates with desired size, shape, and properties have been increasing exponentially owing to their potential applications in molecular sensors, molecular cargos, molecular recognition, and catalysis. The introduction of the organic motifs and metal complexes as a spacer provides functionality to the metalloarchitecture. This review mainly focusses on newly evolving spacer based ligands employed to yield simple to high‐order metallosupramolecular assemblies using straight‐forward approaches. The new spacers including corannulene, organic cyclic framework, bicyclic organic motifs, aliphatic chain, metalloligands, triarylboron, BODIPY, azaphosphatrane, phosphine, and thio/selenophosphates offer a great set of properties and in‐built functionalities to the metalloarchitectures which are discussed in this review.

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Mechanical vs Electronic Strain: Oval-Shaped Alkynyl-Pt(II)-Phosphine Macrocycles

Abstract: Pyridine-terminated molecular rods and either (i) the cis-(dppp)(

Cited by 6 publications

References 42 publications

Mechanical vs Electronic Strain: Calculated Configurations of Alkynyl-Pt(II)-Phosphine Macrocycles

Mechanical vs Electronic Strain: Calculated Configurations of Alkynyl-Pt(II)-Phosphine Macrocycles

Topical progress in medicinal applications of self‐assembled organoplatinum complexes using diverse Pt(II)‐ and N‐based tectons

Emerging Spacers‐Based Ligands for Supramolecular Coordination Complexes

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