Poster Session 2, Wednesday, 18:30-21:30 Yellow Hall

The International Conference on Science and Technology of Synthetic Metals 2016

69

W-8-24 Photo-physical and theoretical investigations of push-pull chromophores derived from

thio-ene-yne compounds via CuAAC

Paul Kautny1, Felix Plasser2, Florian Glöcklhofer1, Thomas Kader1, Berthold Stöger1, Daniel Lumpi1

and Johannes Fröhlich1 1TU Wien, 2University of Vienna

W-8-25 Development of Functional Poly(tetraarylethene)s with In Situ Generated AIEgens by

Three-Component Polymerization of Aryl Diiodides, Internal Diynes and Grignard Reagents

Zijie Qiu, Jacky W. Y. Lam and Ben Zhong Tang

The Hong Kong University of Science and Technology

W-8-26 Synthesis and Characterization of Novel Carboline based Annulated Arylamines

T. Kader, P. Kautny, E. Horkel and J. Fröhlich

Institute of Applied Synthetic Chemistry, TU Wien

W-8-27 Synthesis and Liquid Crystal Properties of a new series of

5,10,15,20-Tetra(4-(N-alkyl)acylphenyl)Porphyrin

Xiaoyuan Zhang, Jinming Zeng, Yaqin Xia and Ping Liu

South China University of Technology

W-8-28 Conformational Polymorphism of a Twisted Conjugated Molecule: Crystal Growth Selectivity and

Fluorescent Mutation

Yuanxiang Xu1,2, Kai Wang3, Yujian Zhang4, Zengqi Xie2, Bo Zou3 and Yuguang Ma2 1Chinese Academy of Engineering physics, 2South China University of Technology, 3Jilin University, 4Huzhou University

W-8-29 Heptagon-Embedded Polycyclic Arenes: Synthesis, Properties and Applications

Xuejin Yang1, Danqing Liu1 and Qian Miao1,2 1The Chinese University of Hong Kong, Shatin, 2Institute of Molecular Functional Materials

W-8-30 Water Involved Inorganic base-promoted Polymerization of Isocyanides with Bromoalkynes: A

Novel and Green Methodology Based on Triple Bond Polymerization

Jie Zhang1, Jing Zhi Sun1, Anjun Qin2 and Ben Zhong Tang1,2,3 1Zhejiang University, 2South China University of Technology, 3The Hong Kong University of Science

and Technology

W-8-31 Highly oriented conjugated polymers by FTM method towards anisotropic photonic and electronic

devices

Manish Pandey, Shuichi Nagamatsu, Shyam S. Pandey and Wataru Takashima

Kyushu Institute of Technology

W-8-32 Solvent effects on the atomistic morphology of bulk heterojunction based organic solar cells: A

computational approach

Photophysical and theoretical investigations of push-pull

chromophores derived from thio-ene-yne compounds via CuAAC

P. Kautny,1* F. Plasser,2 F. Glöcklhofer,1 T. Kader,1 B. Stöger,3 D. Lumpi,1 J. Fröhlich1 1 Institute of Applied Synthetic Chemistry, TU Wien, Austria; 2 Institute of Theoretical Chemistry, University of Vienna, Austria; 3 Institute of

Chemical Technologies and Analytics, TU Wien, Austria; email: paul.kautny@tuwien.ac.at

Motivation

[1] D. Lumpi, B. Stöger, C. Hametner, F. Kubel, G. Reider, H. Hagemann, A. Karpfen, J. Fröhlich, CrystEngComm, Vol. 13, No. 24, (2011), pp 7194-7197.

[2] D. Lumpi, F. Glöcklhofer, B. Holzer, B. Stöger, C. Hametner, G. Reider, J. Fröhlich, Crystal Growth & Design, Vol. 14, No. 3, (2014), pp 1018-1031.

[3] TDDFT/PBE0/6-31+G*.

Recently we introduced 1,2,3-triazoles derived from thio-ene-yne

compounds by copper-catalyzed azide-alkyne cycloaddition (CuAAC) as

potential nonlinear optical (NLO) materials (Scheme 1) [1,2].

Scheme 1. Synthesis of NLO active CuAAC product 3 [1].

Materials related to 3 allow for a broad range of molecular modifications due to

double bond isomerization, sulfur oxidation and the possibility to selectively

synthesize 1,4- as well as 1,5-substituted 1,2,3-triazoles (Scheme 2). Within this work

we investigated the impact of these systematic structural modifications on the

properties of push-pull chromophores derived from 1a to characterize this particular

building block for applications in materials chemistry.

Scheme 2. Potential modifications of the molecular structure of 3.

Synthesis

Characterization

Scheme 3. Synthesis of target

compounds 3a-g. i: CuSO4*5H2O,

sodium-ascorbate, KF, t-BuOH/H2O (1:1),

150 °C. ii: [CpRuCl]4, DMF, 110 °C. iii:

DMDO (1 eq.)., acetone, -40 25 °C. iv:

DMDO (2.5 eq.)., acetone, 25 °C.

Figure 1. Molecular structures of ZMSM-

14TPA (left) and ZMSM-15TPA (right); C,

N and S atoms are represented by gray,

blue and yellow ellipsoids drawn at 90%

probability levels, H atoms by spheres of

arbitrary radius.

• ZMSM-14TPA and EMSM-14TPA exhibit the same photophysical behavior

• Gradual redshift with sulfur oxidation

• Decreased redshift for EMSO2M-14TPA compared to ZMSO2M-14TPA

• 1,5-derivatives strongly redshifted

• Increased charge-transfer for increased sulfur oxidation

• Lower degree of charge-transfer for E derivatives

• No enhancement of charge-transfer for 15 derivatives upon oxidation

Figure 2. UV/Vis absorption and photoluminescence spectra in Et2O.

Figure 3. Lippert-Mataga plots of the compounds under investigation.

Figure 4. NTOs of ZMSM-14TPA (top) and

EMSM-14TPA (bottom). Primary hole NTO (left)

and primary electron NTO (right). [3]

Figure 5. NTOs of ZMSO2M-14TPA (top) and

EMSO2M-14TPA (bottom). Primary hole NTO

(left) and primary electron NTO (right). [3]

• Identical distribution of NTOs for ZMSM-14TPA and

EMSM-14TPA

• Expansion of primary electron NTO onto the SO2

group in ZMSO2M-14TPA explains increased charge-

transfer and redshift

→ fully tunable building block