트리에틸렌 글리콜 치환된 함금속 나프탈로시아닌의 합성과 근적외 흡수 특성 연구

한성훈; 고팔 발라무루간; 장재웅; 손법용; 팜티누구엣; 이승걸; 박종승; Seong-Hun Han; Gopal Balamurugan; Jae Woong Jang; Fayong Sun; Nguyet N. T. Pham; Seung Geol Lee; Jong S. Park

Polymer(Korea), Vol.45, No.6, 881-889, November, 2021

DOI10.7317/pk.2021.45.6.881 Export Citation

트리에틸렌 글리콜 치환된 함금속 나프탈로시아닌의 합성과 근적외 흡수 특성 연구

Synthesis and NIR Absorption Properties of Triethylene Glycol Substituted Metallo-Naphthalocyanines

한성훈¹, 고팔 발라무루간¹, 장재웅¹, 손법용¹, 팜티누구엣¹, 이승걸^{1, 2}, 박종승^{1, 2, †}

¹부산대학교 응용화학공학부
²부산대학교 유기소재시스템공학과

Seong-Hun Han¹, Gopal Balamurugan¹, Jae Woong Jang¹, Fayong Sun¹, Nguyet N. T. Pham¹, Seung Geol Lee^{1, 2}, and Jong S. Park^{1, 2, †}

¹School of Chemical Engineering, Pusan National University, Busan 46241, Korea
²Department of Organic Material Science and Engineering, Pusan National University, Busan 46241, Korea

E-mail:

초록

다양한 전이 금속의 존재하에서 트리에틸렌 글리콜(TEG) 치환체를 가지는 함금속 나프탈로시아닌 유도체(MNPcs)을 합성하고, 이들의 광학적 및 근적외(NIR) 영역에서 흡수 특성을 조사하였다. UV-Vis 스펙트럼 측정 결과에 따르면 MNPcs는 나프탈로시아닌 구조 주변부에 부가된 페닐링과 비주변부(non-peripheral) 위치에 치환된 전자주게 치환체로 인해 NIR 영역에서 강한 흡수 특성을 나타내었다. 또한, MNPcs의 최대 흡수파장은 중앙부 금속의 종류에 따라 780에서 950 nm까지 광범위하게 조정할 수 있었다. 또한, 친수성이 강한 TEG 치환체가 존재함에 따라 극성 용매에서의 용해도와 고분자 매트릭스에 대한 상용성이 크게 증진하는 효과를 나타내었다. 높은 NIR 영역 흡수 및 가시광 투과도를 보이는 MNPc의 특성을 이용하여 근적외 차단 필름을 제조하였다. 니켈-나프탈로시아닌(nickel naphthalocyanine)을 포함하여 근적외 차단 필름을 제조하였을때 안티몬 주석 산화물(ATO) 단독 대비 가시광선 투과성은 그대로 유지하면서 근적외 차단 성능을 향상할 수 있는 것으로 확인되었다. 상기 결과로 보건데 근적외 차단 물질로서의 함금속 나프탈로시아닌의 효능을 확인할 수 있으며, 이는 근적외 흡수성과 극성 매체에 대해 상용성을 동시에 발휘하는 것에 기인하는 것이다.

Naphthalonitrile substituted with triethylene glycol (TEG) in the presence of transition metals synthesized a series of metallo-naphthalocyanine derivatives (MNPcs), and it was investigated that the optical and near-infrared (NIR) absorption properties. In UV-Vis spectra measurements, these MNPcs exhibited strong absorption in the NIR regions because of the annulated benzene ring of naphthalocyanine and highly electron-donating substituents attached at the non-peripheral positions. The absorption wavelength of MNPcs was effectively adjusted in NIR ranges from 780 to 950 nm by inserting various central metals. Additionally, the presence of TEG-substituents in MNPcs significantly enhanced the solubility in highly polar solvents and the compatibility with the polymer matrix. NIR blocking films were fabricated for taking advantage of high NIR absorption and visible transmittance. When NIR film was fabricated with nickel-napthalocyanine, it was confirmed that the NIR cutting property can be improved while maintaining the visible light transmittance compared to the antimony tin oxide (ATO). From the observations, the feasibility of designed MNPcs as an effective NIR blocking material was evidenced, which is attributed to its strong NIR absorption and compatibility in the polar mediums.

Keywords:naphthalocyanine;triethylene glycol;near-infrared blocking film;near-infrared filter

[References]

Nguyen TKN, Renaud A, Wilmet M, et al., J. Mater. Chem. C, 5, 10477 (2017)
Medina I, Newton E, Kearney MR, Mulder RA, Porter WP, Stuart-Fox D, Nat. Commun., 9, 3610 (2018)
Lamnatou C, Chemisana D, Renew. Sust. Energ. Rev., 18, 271 (2013)
Xu XY, Zhang WL, Hu Y, Wang YH, Lu L, Wang SJ, Sol. Energy Mater. Sol. Cells, 168, 119 (2017)
Yao Y, Zhang L, Chen Z, Cao C, Gao Y, Luo H, Ceram. Int., 44, 13469 (2018)
Abendroth T, Schumm B, Alajlan SA, Almogbel AM, Mader G, Hartel P, Althues H, Kaskel S, Thin Solid Films, 624, 152 (2017)
Xingyu X, Lin L, Energy Procedia, 105, 4836 (2017)
Fang D, Yu H, Dirican M, et al., Carbohydr. Polym., 266, 118175 (2021)
Krishnakumar T, Jayaprakash R, Pinna N, Phani A, Passacantando M, Santucci S, J. Phys. Chem. Solids, 70, 993 (2009)
Gould R, Coord. Chem. Rev., 156, 237 (1996)
Son H , Ji JH, Jeong JH, Han SH, Koh JH, Park JS, Polym. Korea, 44, 301 2020.
Son HS, Yang MH, Mutyala AK, Chang DW, Park JS, Dyes Pigment., 162, 662 (2019)
van Leeuwen M, Beeby A, Fernandes I, Ashworth SH, Photochem. Photobiol. Sci., 13, 62 (2014)
Sakamoto K, Ohno-Okumura E, Kato T, Soga H, J. Porphyr. Phthalocya., 14, 47 (2010)
Hirao A, Akiyama T, Okujima T, Yamada H, Uno H, Sakai Y, Aramaki S, Ono N, Chem. Commun., 4714 2008.
Rawling T, McDonagh A, Coord. Chem. Rev., 251, 1128 (2007)
Taratula O, Schumann C, Duong T, Taylor KL, Taratula O, Nanoscale, 7, 3888 (2015)
Choi MT, Li PP, Ng DK, Tetrahedron, 56, 3881 (2000)
Batat P, Bayar M, Pur B, Coker E, Ahsen V, Yuksel F, Demirel AL, Phys. Chem. Chem. Phys., 18, 15574 (2016)
Isago H, Kagaya Y, Matsushita A, Chem. Lett., 33(7), 862 (2004)
Kudrik EV, Afanasiev P, Bouchu D, Sorokin AB, J. Porphyr. Phthalocya., 15, 583 (2011)
Kang IS, Lee TJ, Seo MJ, Hwang SY, Park NK, Lee SW, Polym. Korea, 43(5), 793 (2019)

[1] Nguyen TKN, Renaud A, Wilmet M, et al., J. Mater. Chem. C, 5, 10477 (2017)

[2] Medina I, Newton E, Kearney MR, Mulder RA, Porter WP, Stuart-Fox D, Nat. Commun., 9, 3610 (2018)

[3] Lamnatou C, Chemisana D, Renew. Sust. Energ. Rev., 18, 271 (2013)

[4] Xu XY, Zhang WL, Hu Y, Wang YH, Lu L, Wang SJ, Sol. Energy Mater. Sol. Cells, 168, 119 (2017)

[5] Yao Y, Zhang L, Chen Z, Cao C, Gao Y, Luo H, Ceram. Int., 44, 13469 (2018)

[6] Abendroth T, Schumm B, Alajlan SA, Almogbel AM, Mader G, Hartel P, Althues H, Kaskel S, Thin Solid Films, 624, 152 (2017)

[7] Xingyu X, Lin L, Energy Procedia, 105, 4836 (2017)

[8] Fang D, Yu H, Dirican M, et al., Carbohydr. Polym., 266, 118175 (2021)

[9] Krishnakumar T, Jayaprakash R, Pinna N, Phani A, Passacantando M, Santucci S, J. Phys. Chem. Solids, 70, 993 (2009)

[10] Gould R, Coord. Chem. Rev., 156, 237 (1996)

[11] Son H , Ji JH, Jeong JH, Han SH, Koh JH, Park JS, Polym. Korea, 44, 301 2020.

[12] Son HS, Yang MH, Mutyala AK, Chang DW, Park JS, Dyes Pigment., 162, 662 (2019)

[13] van Leeuwen M, Beeby A, Fernandes I, Ashworth SH, Photochem. Photobiol. Sci., 13, 62 (2014)

[14] Sakamoto K, Ohno-Okumura E, Kato T, Soga H, J. Porphyr. Phthalocya., 14, 47 (2010)

[15] Hirao A, Akiyama T, Okujima T, Yamada H, Uno H, Sakai Y, Aramaki S, Ono N, Chem. Commun., 4714 2008.

[16] Rawling T, McDonagh A, Coord. Chem. Rev., 251, 1128 (2007)

[17] Taratula O, Schumann C, Duong T, Taylor KL, Taratula O, Nanoscale, 7, 3888 (2015)

[18] Choi MT, Li PP, Ng DK, Tetrahedron, 56, 3881 (2000)

[19] Batat P, Bayar M, Pur B, Coker E, Ahsen V, Yuksel F, Demirel AL, Phys. Chem. Chem. Phys., 18, 15574 (2016)

[20] Isago H, Kagaya Y, Matsushita A, Chem. Lett., 33(7), 862 (2004)

[21] Kudrik EV, Afanasiev P, Bouchu D, Sorokin AB, J. Porphyr. Phthalocya., 15, 583 (2011)

[22] Kang IS, Lee TJ, Seo MJ, Hwang SY, Park NK, Lee SW, Polym. Korea, 43(5), 793 (2019)