KR100663887B1 - Water-soluble supramolecular platinum complexes and process for preparation thereof - Google Patents
Water-soluble supramolecular platinum complexes and process for preparation thereof Download PDFInfo
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Abstract
본 발명은 초고분자 백금 착화합물(water-soluble supramolecular platinum complexes) 및 그 제조방법에 관한 것으로, 본 발명에 따라 사염화백금칼륨염(potassium tetrachloroplatinate, K2(PtCl4))과 폴리(옥시알킬렌)기를 가진 알킬아민(poly(oxyalkylene)alkylamine)을 반응시켜 합성한 사아민화백금 착이온([Pt(NH2R)4]2+)에 다시 K2(PtCl4)를 반응시켜 제조한 백금 착화합물은 수용성 및 우수한 반도체로서의 전기 전도성을 나타내므로, 생의학(biomedical) 및 반도체(semiconducting materials) 분야에서 산업적으로 유용하게 활용될 수 있다.The present invention relates to ultra-high molecular weight complex (water-soluble supramolecular platinum complexes) and a method for producing the same. According to the present invention, potassium tetrachloroplatinate (K 2 (PtCl 4 )) and poly (oxyalkylene) groups with an alkyl amine (poly (oxyalkylene) alkylamine) the Saha folk platinum complex ion synthesized by reacting ([Pt (NH 2 R) 4] 2+) again with K 2 platinum complex prepared by reacting (PtCl 4) is water-soluble And because it exhibits excellent electrical conductivity as a semiconductor, it can be usefully used industrially in the field of biomedical and semiconductor (semiconducting materials).
Description
도 1은 실시예 1에서 제조한 수용성 백금 착화합물(platinum complexes)의 열 중량 분석(thermogravimetric analysis) 결과이고, 1 is a result of thermogravimetric analysis of water-soluble platinum complexes prepared in Example 1,
도 2는 수용성 백금 착화합물의 UV-가시 분광 분석(UV-visible spectrum) 결과이고, 2 is a UV-visible spectrum of the water-soluble platinum complex (UV-visible spectrum) results,
도 3은 수용성 백금 착화합물의 퓨리에 전환 적외선 분광 분석(FT-IR) 결과이고, 3 is a Fourier transform infrared spectroscopy (FT-IR) result of the water-soluble platinum complex,
도 4는 수용성 백금 착화합물의 온도 역수(inverse temperature)에 따른 전도도(conductivity) 로그 그래프이다. 4 is a logarithmic conductivity graph of the water soluble platinum complex with the inverse temperature.
본 발명은 수용성 초고분자 백금 착화합물(water-soluble supramolecular platinum complexes) 및 그 제조방법에 관한 것이다.The present invention relates to water-soluble supramolecular platinum complexes and a method for preparing the same.
백금 착화합물은 백금 금속에 이온이나 분자가 배위결합한 백금 착이온을 포함하는 화합물을 의미하며, 최근에는 백금 착화합물의 항암효과 및 나노구조의 전도성으로 인하여 생의학 및 반도체 등의 여러 산업 분야에서 많은 관심의 대상이 되고 있다. Platinum complex compound refers to a compound containing a platinum complex ion in which ions or molecules are coordinated to a platinum metal. Recently, due to the anticancer effect and the conductivity of nanostructures, platinum complex compounds are of interest to many industries such as biomedical and semiconductors. It is becoming.
특히, 본 발명의 백금 착화합물 구조의 원조격인 마그너스 녹색 염(Magnus' green salt, [Pt(NH3)4][PtCl4])은 200년 전 처음으로 합성되었으며, Pt를 금속 주쇄(metallic main-chain)로 하여 자가 결합된 독특한 초분자 구조(self-assembled supramolecular structure)로 반-일차원 구조(quasi-one-dimensional structure)의 상대적으로 짧은 Pt-Pt 결합으로 반도체로서의 특성을 가진다. 그러나, [Pt(NH3)4][PtCl4] 및 이의 유도체인 [Pt(NH2CH3)
4][PtCl4]는 물 및 통상의 유기 용제에 불용성을 나타내었고, 이를 극복하기 위해 R로 헵틸(heptyl) 내지 테트라데실(tetradecyl) 범위의 알킬기를 포함하는[Pt(NH2R)4][PtCl4] 유도체들이 연구되었으나, Pt-Pt사이의 공간이 넓어짐으로 인해 녹색 염 고유의 성질을 잃고, 분홍색(pink salts)의 절연체가 되는 문제점이 발생하였다. 따라서, 이러한 물질들의 다양한 응용 가능성에도 불구하고 가공 및 산업화에 상당한 제약이 있어 왔다(M.Fontana 외, Chem. Mater., 14, 1730-1735, 2002).In particular, Magnus' green salt ([Pt (NH 3 ) 4 ] [PtCl 4 ]), which is a precursor of the platinum complex structure of the present invention, was synthesized for the
본 발명의 목적은 수용성이면서 반도체로서의 전도성이 우수한 백금 착화합 물 및 그 제조방법을 제공하는 것이다.An object of the present invention is to provide a platinum complex and a method for producing the same, which are water soluble and excellent in conductivity as a semiconductor.
상기 목적에 따라, 본 발명에서는 하기 화학식 1의 화합물을 반복단위로 가진 수용성 초고분자 백금 착화합물을 제공한다:In accordance with the above object, the present invention provides a water-soluble ultra-high molecular platinum complex having a compound of
상기 식에서 R은 폴리(옥시알킬렌)기를 가진 C1 내지 C5 알킬아민의 잔기(moiety)를 의미한다.In the formula, R means a moiety of C 1 to C 5 alkylamine having a poly (oxyalkylene) group.
상기 다른 목적에 따라, 본 발명에서는 상기 수용성 백금 착화합물의 제조방법을 제공한다.According to another object, the present invention provides a method for producing the water-soluble platinum complex compound.
이하, 본 발명을 상세히 설명한다.Hereinafter, the present invention will be described in detail.
본 발명자들은 수용성이면서도 반도체로서의 전기 전도성이 우수한 백금 착 화합물([Pt(NH2R)4][PtCl4])을 개발하기 위해 예의 연구한 결과, 사염화백금칼륨염(potassium tetrachloroplatinate, K2(PtCl4))과 폴리(옥시알킬렌)기를 가진 알킬아민(poly(oxyalkylene)alkylamine)을 반응시켜 제조한 상기 화학식 1의 백금 착화합물이 수용성 및 우수한 반도체로써의 전기 전도성을 나타냄을 발견하였다.The present inventors have found that water-soluble, yet is excellent in electrical conductivity of platinum complex compound as the semiconductor ([Pt (NH 2 R) 4] [PtCl 4]) for example The results tetrachloride platinum potassium salt which to develop (potassium tetrachloroplatinate, K 2 (PtCl It was found that the platinum complex compound of
본 발명의 화학식 1의 수용성 백금 착화합물은 백금을 금속 주쇄(metallic main-chain)로 하여 사아민화백금 착(+)이온([Pt(NH2R)4]2+) 및 사염화백금 착(-)이온([PtCl4]2-)이 자가결합된 독특한 초분자 구조(self-assembled supramolecular structure)로 반도체로서의 전도성을 가지고 있으며, 특히, 사아민화백금 착이온에 존재하는 산소로 인해 우수한 수용성을 나타낸다. The water-soluble platinum complex compound of the formula (1) of the present invention comprises platinum tetraamine complex (+) ions ([Pt (NH 2 R) 4 ] 2+ ) and platinum tetrachloride complex (-) using platinum as a metallic main-chain. A unique self-assembled supramolecular structure in which ions ([PtCl 4 ] 2− ) are self-bonded, has conductivity as a semiconductor, and exhibits excellent water solubility due to the oxygen present in the platinum tetraamine complex ion.
본 발명에 따른 수용성 백금 착화합물은 하기 반응식 1 및 2와 같이 사염화백금칼륨염을 폴리(옥시알킬렌)기를 가진 알킬아민과 반응시켜 합성한 사아민화백금 착이온에 다시 사염화백금칼륨염을 반응시킴으로써 제조할 수 있다. The water-soluble platinum complex compound according to the present invention is prepared by reacting the platinum tetrachloride potassium ion with the platinum tetrachloride synthesized by reacting the platinum tetrachloride salt with an alkylamine having a poly (oxyalkylene) group as shown in
상기 반응식 1 및 2에서 R은 폴리(옥시알킬렌)기를 가진 알킬아민의 잔기이다.R in
구체적으로, 화학식 1의 수용성 초고분자 백금 착화합물을 제조하기 위하여, 본 발명에서는 상기 반응식 1에서와 같이, 화학식 2의 사염화백금칼륨염(potassium tetrachloroplatinate, K2(PtCl4))과 폴리(옥시알킬렌)알킬아민을 반응시켜 화학식 3의 사아민화백금 착이온([Pt(NH2R)4]2+)을 얻은 후, 상기 반응식 2에서와 같이, 생성된 [Pt(NH2R)4]2+에 다시 K2(PtCl4)를 반응시키는 과정을 포함한다.Specifically, in order to prepare a water-soluble ultra-high molecular platinum complex of formula (1), in the present invention, as shown in
이때, 반응식 1의 과정에서 사용되는 폴리(옥시알킬렌)기를 가진 알킬아민은 하기 화학식으로 나타낼 수 있다:At this time, the alkylamine having a poly (oxyalkylene) group used in the process of
상기 식에서 R1 및 R2는 각각 독립적으로 C1 내지 C5의 선형 또는 분지형 알킬렌, W는 H 또는 NH2, n은 2 내지 50의 정수이며, 이때, 상기 반복단위 내 R2는 서로 동일하거나 다를 수 있다. Wherein R 1 and R 2 are each independently C 1 to C 5 linear or branched alkylene, W is H or NH 2 , n is an integer of 2 to 50, wherein R 2 in the repeating unit It can be the same or different.
상기 폴리(옥시알킬렌)기를 가진 알킬아민의 구체적 예로는 , (R은 H 또는 CH3) 또는 (a+b+c는 2 내지 50의 정수)등이 있다.Specific examples of the alkylamine having the poly (oxyalkylene) group include , (R is H or CH 3 ) or (a + b + c is an integer of 2 to 50) and the like.
상기 착이온 형성 반응에 사용되는 사염화백금칼륨염:폴리(옥시알킬렌)아민의 몰비는 1:1 내지 1:10 범위, 바람직하게는 1:2 내지 1:4 범위일 수 있으며, 반응은 50 내지 60℃, 바람직하게는 55℃에서 10 내지 30시간, 바람직하게는 22 내지 24시간 동안 수행할 수 있다.The molar ratio of platinum tetrachloride potassium: poly (oxyalkylene) amine used in the complex ion formation reaction may be in the range of 1: 1 to 1:10, preferably in the range of 1: 2 to 1: 4, and the reaction is 50 To 60 ° C., preferably 55 ° C., for 10 to 30 hours, preferably 22 to 24 hours.
또한, 반응식 2의 과정에서, 생성된 [Pt(NH2R)4]2+에 추가로 첨가하는 K2(PtCl4)의 양은, 반응식 1의 과정에서 사용된 K2(PtCl4) 몰 대비 0.5 내지 4배, 바람직하게는 1 내지 2배로 사용할 수 있으며, 이때 반응은 20 내지 30℃, 바람직하 게는 25℃에서 10 내지 50시간, 바람직하게는 20 내지 40시간 동안 수행할 수 있다.In addition, in the process of Scheme 2, the amount of K 2 (PtCl 4 ) added to [Pt (NH 2 R) 4 ] 2+ additionally, compared to the mole of K 2 (PtCl 4 ) used in the process of
본 발명을 이하 실시예에 의해 상세히 설명한다.The invention is illustrated in detail by the following examples.
단, 하기 실시예는 본 발명을 예시하는 것일 뿐, 본 발명의 내용이 하기 실시예에 한정되는 것은 아니다.However, the following examples are merely to illustrate the invention, but the content of the present invention is not limited to the following examples.
<실시예 1><Example 1>
50 ㎎(0.12 mM)의 K2(PtCl4)를 10 ㎖의 물에 녹여 55℃에서 교반한 후, 이 용액에 59 ㎕(0.24 mM)의 폴리(옥시프로필렌)이소프로필디아민(poly(oxypropylene)isopropyldiamine)을 첨가하여 55℃에서 24시간 동안 교반하면서 반응시켜 사아민화백금 착이온([Pt(NH2R)4]2+)을 생성시켰다. 이 반응생성물에 0.12 mM K2 (PtCl4) 10 ㎖을 첨가한 다음, 100 ㎖의 탈 이온수(deionized water)와 혼합시켜 한외(限外) 여과 셀(ultrafiltration cell)로 옮겼다. 이를 상온에서 24시간 동안 교반하면서 막(membrane)을 이용한 여과로 반응하지 않은 폴리머 및 불순물을 제거하였다. 여과 후, 생성된 용액은 동결건조(freeze-dry)로 물을 제거시켜 본 발명에 따른 수용성 백금 착화합물([Pt(NH2R)4][PtCl4])을 제조하였다. 50 mg (0.12 mM) of K 2 (PtCl 4 ) was dissolved in 10 ml of water, stirred at 55 ° C, and then 59 µl (0.24 mM) of poly (oxypropylene) isopropyldiamine (poly (oxypropylene)) in this solution. isopropyldiamine) was added and reacted with stirring at 55 ° C. for 24 hours to produce platinum tetraamine complex ion ([Pt (NH 2 R) 4 ] 2+ ). 10 ml of 0.12 mM K 2 (PtCl 4 ) was added to the reaction product, which was then mixed with 100 ml of deionized water and transferred to an ultrafiltration cell. This was stirred for 24 hours at room temperature to remove unreacted polymer and impurities by filtration using a membrane (membrane). After filtration, the resulting solution was freeze-dryed to remove water to prepare a water-soluble platinum complex ([Pt (NH 2 R) 4 ] [PtCl 4 ]) according to the present invention.
열중량 분석(thermogravimetric analysis, TGA)Thermogravimetric analysis (TGA)
상기 실시예 1에서 제조한 수용성 백금 착화합물의 열안정성을 TGA 분석으로 확인하였다. The thermal stability of the water-soluble platinum complex compound prepared in Example 1 was confirmed by TGA analysis.
그 결과, 도 1에 나타난 바와 같이, 160℃ 및 270℃에서 나타난 두 번의 분해로 본 발명의 수용성 백금 착화합물에 [Pt(NH2R)4]2+ 및 [PtCl4 ]2-가 존재하고 있음을 확인하였으며, 300℃ 내지 800℃의 고온에서도 수용성 백금 착화합물 중량의 45%가 남아있음을 확인하였다. As a result, as shown in FIG. 1, [Pt (NH 2 R) 4 ] 2+ and [PtCl 4 ] 2- are present in the water-soluble platinum complex compound of the present invention by two decompositions at 160 ° C. and 270 ° C. It was confirmed that 45% of the water-soluble platinum complex weight remained at a high temperature of 300 ° C to 800 ° C.
자외선-가시광선 분광법(UV-visible spectrum)UV-visible spectrum
상기 실시예 1에서 제조한 수용성 백금 착화합물을 자외선-가시광선 분광법으로 분석한 결과, 도 2에서 나타낸 바와 같이, 파장 292 ㎚에서 최대 흡수율을 나타내었다. 이러한 흡수율은, 개개의 배위 단위의 분광(spectra of individual coordination unit) 없이, [PtCl4]2- 쪽 백금 원자의 5dz2 전자궤도로부터 [Pt(NH2R)4]2+ 쪽 백금 원자의 6pz 전자궤도로의 전하 이동(charge transfer)을 의미한다. As a result of analyzing the water-soluble platinum complex compound prepared in Example 1 by ultraviolet-visible spectroscopy, as shown in FIG. 2, the maximum absorption was shown at a wavelength of 292 nm. This absorptivity is calculated from the 5dz2 orbital of the [PtCl 4 ] 2- side platinum atom without the spectra of individual coordination unit, and the 6pz electron of the [Pt (NH 2 R) 4 ] 2+ side platinum atom. It means the charge transfer to orbit.
FT-IR 분광법FT-IR spectroscopy
실시예 1에서 제조한 수용성 백금 착화합물을 FT-IR 분광법으로 분석한 결 과, 도 3에 나타낸 바와 같이, N-H, C-H 및 C-O의 결합은 각각의 팽창 피크(stretching peak) 3213, 2856 및 1078 ㎝-1에서 확인되었으며, Pt-N의 결합은 588 ㎝-1의 피크로 확인되었다. 따라서, 목적하는 화합물이 제조되었음을 알 수 있다.As a result of analyzing the water-soluble platinum complex prepared in Example 1 by FT-IR spectroscopy, as shown in FIG. 3, the binding of NH, CH, and CO was shown at the stretching peaks 3213, 2856, and 1078 cm −, respectively. It was confirmed at 1 , the binding of Pt-N was confirmed with a peak of 588 cm -1 . Thus, it can be seen that the desired compound was prepared.
전도도(conductivity) 분석Conductivity Analysis
상기 실시예 1에서 제조한 수용성 백금 착화합물의 전도율(conductivity)을 온도 역수(inverse temperature, 1/T)에 따라 측정하여 그 결과를 도 4에 로그로 나타내었다. Conductivity of the water-soluble platinum complex compound prepared in Example 1 was measured according to an inverse temperature (1 / T), and the results are shown in logarithmic manner in FIG. 4.
도 4에 나타난 바와 같이, 본 발명의 수용성 백금 착화합물이 반도체의 특성인 온도 역수에 선형(linear)으로 반비례하는 전도율을 가짐을 알 수 있다. As shown in FIG. 4, it can be seen that the water-soluble platinum complex compound of the present invention has a conductivity that is inversely proportional to the temperature inverse of the characteristics of the semiconductor.
상기에서 살펴본 바와 같이, 본 발명에 따라 사염화백금칼륨염(potassium tetrachloroplatinate, K2(PtCl4))과 폴리(옥시알킬렌)알킬아민(poly(oxyalkilene)alkylamine)을 반응시켜 제조한 수용성 백금 착화합물은 열적 안정성 및 반도체로서의 전기 전도성이 우수하며 수용성을 나타내므로, 생의학 및 유기 반도체 등의 다양한 산업에 유용하게 활용될 수 있다.As described above, according to the present invention, a water-soluble platinum complex compound prepared by reacting potassium tetrachloroplatinate (K 2 (PtCl 4 )) with poly (oxyalkylkilene) alkylamine Because of excellent thermal stability and electrical conductivity as a semiconductor and water solubility, it can be usefully used in various industries such as biomedical and organic semiconductors.
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