Quantum-chemical Investigations of Structures and Stabilities of Ethynyl-or Ethenyl-expanded [n]-Prismanes

Quantum-chemical calculations on some derivatives of [n]-prismanes expanded by ethynyl or ethenyl groups have been performed using density functional theory （DFT） method.Their geometric structures,electronic structures,vertical ionization potentials and vertical electron affinities have been obtained at the B3LYP/6-31G＊＊ level of theory.Meanwhile,the total strain energy has been investigated in detail and compared with [n]-prismane and other derivatives.The present paper has also computed the enthalpies of formation for different isomers so as to evaluate their thermal stabilities.

Quantum mechanic study on cyclic molecul formation from ethynyl radical （C2H） and ethyne （C2H2）

The first cyclic molecule formation reactions from ethyne （C2H2）, initiated by ethynyl radical （C2H）, were studied by theoretical quantum mechanic. The study included the competition reaction between structure re-arrangement for the favourable ring-closure mechanism and ethyne addition in each step. The analysis was done by evaluating the energy difference of activation （AE）, entalphy （AH）, Gibbs （AG） of the optimized stable and transition molecules. The reaction temperatures were set at normal （T = 298 K） and combustion （T = 1200 K） condition.

Solar cells based on doubly concerted companion dyes with the efficiencies modulated by inserting an ethynyl group at different positions

To develop efficient sensitizers for dye-sensitized solar cells(DSSCs),we recently reported doubly concerted companion(DCC)dye XW83 with a wrapped porphyrin sub-dye unit linked to an organic sub-dye unit through a flexible chain,which exhibits panchromatic absorption and excellent anti-aggregation ability.To further improve the absorption,we herein report XW87 and XW88 by inserting an ethynyl group into the organic sub-dye unit of XW83 near the donor and acceptor,respectively.For the corresponding organic dyes Z3 and Z4,the introduced ethynyl group improves their absorption,but induces aggravated charge recombination,leading to lowered power conversion efficiencies(PCEs).Similar to the organic dyes,the introduced ethynyl group improves the absorption of DCC dyes XW87 and XW88 as well.In addition,the ethynyl group near the acceptor of the organic sub-dye unit can be well protected by the long wrapping chains from the porphyrin unit.As a result,XW88 affords the highest JSC(21.84 mA/cm^(2)),V_(OC)(782 mV)and PCE(12.2%)among the DCC dyes.These results provide an effective method for developing efficient DSSC dyes by inserting an ethynyl group at a suitable position of a DCC dye.

Ethynyl-linked perylene bisimide based electron acceptors for non-fullerene organic solar cells

In this work, star-shaped perylene bisimide（PBI） derivatives with spiro-aromatic cores linked with ethynyl units were developed as electron acceptors for non-fullerene organic solar cells. The ethynyl linkers were found to enhance the planarity of the conjugated backbone, resulting in high electron mobilities and near-infrared absorption. The ethynyl-linked PBI acceptors showed high power conversion efficiencies（PCEs） up to 4.27% due to the high short-circuit current density（Jsc） of 8.52 mA/cm^2 and fill factor（FF） of 0.59, while the PBI acceptor without ethynyl units provided a low PCE of 3.57% in nonfullerene solar cells. The results demonstrate that ethynyl units can be applied into designing new PBI electron acceptors with improved charge transport properties and photovoltaic performance.

1,2,5,6-Naphthalenediimide-based Conjugated Copolymers Linked by Ethynyl Units

Two copolymers of P1 and P2 comprising benzothiadiazole, 1,4-bis（dodecyloxy）-benzene units were synthesized by Sonogashira coupling polymerization based on ethynyl-linked 1,2,5,6-naphthalenediimide. Their thermal, optical, electrochemical as well as charge transport properties were studied. Bottom-gate top-contact organic field-effect transistors （OFETs） measurements of P1 and P2 thin films showed different charge transport behaviors. P1 displayed pure electron transport behaviors in OFETs with electron mobility up to 10^-3 cm^2·V-1·s^-1, while P2 exhibited hole transport features. The molecular structure analysis revealed that the structure of P1 has the acceptor-linker-acceptor＇ （A-L-A＇） characteristic, and P2 possesses the donor-linker-acceptor （D-L-A） structure feature. The results demonstrate that different molecular structures lead them to have distinct charge transport behaviors. In particular, the first pure electron transport copolymer in OFETs based on 1,2,5,6-naphthalenediimide is achieved.