The novel link between planar möbius aromatic and third order nonlinear optical properties of metal–bridged polycyclic complexes

Wang, Li; Ye, Jin-Ting; Wang, Hong-Qiang; Xie, Haiming; Qiu, Yong‐Qing

doi:10.1038/s41598-017-10739-7

Cited by 23 publications

(20 citation statements)

References 61 publications

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“…The properties of the carbolong complexes were also investigated. 8,10,13,40 We first examined the photoluminescence properties of osmapentalyne 2a. As shown in Figure 12, excitation at 440 nm in the visible region leads to near-infrared (NIR) emission by 2a, in which the Stokes shift reaches 320 nm.…”

Section: Properties and Applications Of Carbolong Speciesmentioning

confidence: 99%

Carbolong Chemistry: A Story of Carbon Chain Ligands and Transition Metals

2018

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The construction of metal-carbon bonds is one of the most important issues of organometallic chemistry. However, the chelation of polydentate ligands to a metal via several metal-carbon bonds is rare. Metallapentalyne, which can be viewed as a 7-carbon (7C) chain coordinated to a metal via three metal-carbon bonds, was first reported in 2013. Although metallapentalyne contains a metal-carbon triple bond in a five-membered ring (5MR) and the bond angle around the carbyne carbon is only 129.5°, metallapentalyne exhibits excellent stability to air, moisture, and heat. Metallapentalyne possesses the rare planar Möbius aromaticity, which is in sharp contrast to the Hückel antiaromaticity in pentalyne. The metal fragment not only relieves the large ring strain present in pentalyne but also results in the transformation of the antiaromaticity in pentalyne to aromaticity in metallapentalyne. With the extension of the carbon chain from 7 to 12 carbon atoms, a series of novel polycyclic frameworks were constructed via the formation of several metal-carbon bonds. Some interesting phenomena were observed for these complexes. For instance, (1) the carbyne carbon of the 7C framework could react with both nucleophilic and electrophilic reagents, leading to the formation of 16- and 18-electron metallapentalenes; (2) σ aromaticity was first observed in an unsaturated system in the 8C framework; (3) two classical antiaromatic frameworks, cyclobutadiene and pentalene, were simultaneously stabilized in the 9C framework for the first time; (4) three fused 5MRs bridged by a metal are coplanar in the 10C framework; (5) the first [2 + 2 + 2] cycloaddition of a late transition metal carbyne complex with alkynes was realized during the construction of an 11C framework; (6) the largest number of carbon atoms coordinated to a metal atom in the equatorial plane was observed in the 12C framework; and (7) sharing of the transition metal by multiple aromatic units has seldom been observed in the metalla-aromatics. Therefore, the term carbolong chemistry has been used to describe the chemistry of these novel frameworks. More interestingly, carbolong complexes exhibit diverse properties, which could lead to potential future applications. As the discovery and creation of molecular fragments lead to advancements in chemistry, medical science, and materials chemistry, these novel polydentate carbon chain chelates might have important influences in these fields due to their facile synthesis, high stability, and unique properties.

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Section: Properties and Applications Of Carbolong Speciesmentioning

confidence: 99%

Carbolong Chemistry: A Story of Carbon Chain Ligands and Transition Metals

2018

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“…For the first time we have achieved the establishment of a direct link of a physical response property (magnetic shielding) to frontier orbital topology (Möbius or Hückel), and in cyclic conjugated systems . Other physical properties, like non‐linear optical (NLO) response, may possess similar dependencies . Most intriguingly, it has been already proposed that several physical observables might be linked to π‐HOMO topology (coarctate Möbius or Hückel) in linear allenes…”

Section: Figurementioning

confidence: 99%

Strict Correlation of HOMO Topology and Magnetic Aromaticity Indices in d‐Block Metalloaromatics

Mauksch

Tsogoeva

2018

Chemistry A European J

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Magnetic aromaticity and antiaromaticity of closed shell metalloaromatics with 4d transition metals (Nb, Tc, Rh) is strictly correlated with the orbital topology (Möbius or Hückel) of their π-HOMO, investigated computationally with DFT methods. A surprisingly simple rule emerged: the metallacycle is aromatic (antiaromatic) when the number of π MOs is even and the π-HOMO is of Möbius (Hückel) topology-and vice versa when the number of π MOs is odd.

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“…Nonlinear optical response is a well studied phenomena and also molecules having high NLO response have great significance because of its wide range of applications in the field of laser physics and photonic devices. Most of the optically active materials show third order non linear optical property because it is the lowest order nonlinear effect . Nonlinear absorption is the change in transmittance with respect to its intensity or fluence.…”

Section: Resultsmentioning

confidence: 99%

A study of structural effects on linear and nonlinear response of bicompartmental Ni (II) Schiff base complexes

Mohan

Sreejith

Kuttippurath

et al. 2019

Applied Organom Chemis

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Herein we investigate imaginary third order NLO activity, optical limiting capability and first hyperpolarizabilities of five Ni (II) salen complexes using experimental and theoretical methods. The complexes are tuned to have different NLO response by changing mainly the diimine spacer group. Out of the compounds reported, the one with o‐phenylene spacer group exhibits the highest NLO activity comparable with that of polymers and semiconductors which is followed by the compound with ethylene spacer unit. The order of activity is a direct function of the degree of π‐delocalization. Further all the tested compounds returned outstanding optical limiting capabilities making them excellent materials for fabrication of such devices. The experimental results were substantiated with frontier orbital calculations carried out using DFT at M06/6‐31G* level of theory and complex with aromatic spacer group exhibits least energy gap and highest activity. The total dipole moment, polarizability and first hyperpolarizability were also calculated at the same level of theory which are also in line with the experimentally observed results.

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The novel link between planar möbius aromatic and third order nonlinear optical properties of metal–bridged polycyclic complexes

Cited by 23 publications

References 61 publications

Carbolong Chemistry: A Story of Carbon Chain Ligands and Transition Metals

Carbolong Chemistry: A Story of Carbon Chain Ligands and Transition Metals

Strict Correlation of HOMO Topology and Magnetic Aromaticity Indices in d‐Block Metalloaromatics

A study of structural effects on linear and nonlinear response of bicompartmental Ni (II) Schiff base complexes

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