JP4573259B2 - Diporphyrin derivatives and polyporphyrin derivatives - Google Patents
Diporphyrin derivatives and polyporphyrin derivatives Download PDFInfo
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- 238000000034 method Methods 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 8
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 5
- 239000003054 catalyst Substances 0.000 claims description 4
- 125000004122 cyclic group Chemical group 0.000 claims description 3
- 229910021645 metal ion Inorganic materials 0.000 claims description 3
- 150000004033 porphyrin derivatives Chemical class 0.000 claims 1
- 239000011701 zinc Substances 0.000 description 21
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 16
- 238000001840 matrix-assisted laser desorption--ionisation time-of-flight mass spectrometry Methods 0.000 description 13
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 12
- 150000001875 compounds Chemical class 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 9
- 150000004032 porphyrins Chemical class 0.000 description 9
- 238000010521 absorption reaction Methods 0.000 description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- -1 porphyrin metal complex Chemical class 0.000 description 6
- 238000000862 absorption spectrum Methods 0.000 description 5
- 239000003153 chemical reaction reagent Substances 0.000 description 5
- PCLIMKBDDGJMGD-UHFFFAOYSA-N N-bromosuccinimide Chemical compound BrN1C(=O)CCC1=O PCLIMKBDDGJMGD-UHFFFAOYSA-N 0.000 description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 229910052725 zinc Inorganic materials 0.000 description 4
- 125000001989 1,3-phenylene group Chemical group [H]C1=C([H])C([*:1])=C([H])C([*:2])=C1[H] 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 150000004696 coordination complex Chemical class 0.000 description 3
- SFPQFQUXAJOWNF-UHFFFAOYSA-N 1,3-diiodobenzene Chemical compound IC1=CC=CC(I)=C1 SFPQFQUXAJOWNF-UHFFFAOYSA-N 0.000 description 2
- HZNVUJQVZSTENZ-UHFFFAOYSA-N 2,3-dichloro-5,6-dicyano-1,4-benzoquinone Chemical compound ClC1=C(Cl)C(=O)C(C#N)=C(C#N)C1=O HZNVUJQVZSTENZ-UHFFFAOYSA-N 0.000 description 2
- BMIBJCFFZPYJHF-UHFFFAOYSA-N 2-methoxy-5-methyl-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pyridine Chemical compound COC1=NC=C(C)C=C1B1OC(C)(C)C(C)(C)O1 BMIBJCFFZPYJHF-UHFFFAOYSA-N 0.000 description 2
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 2
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 2
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000006870 function Effects 0.000 description 2
- 230000005525 hole transport Effects 0.000 description 2
- 229910052751 metal Chemical class 0.000 description 2
- 239000002184 metal Chemical class 0.000 description 2
- 238000006263 metalation reaction Methods 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- LFMWZTSOMGDDJU-UHFFFAOYSA-N 1,4-diiodobenzene Chemical compound IC1=CC=C(I)C=C1 LFMWZTSOMGDDJU-UHFFFAOYSA-N 0.000 description 1
- 125000001140 1,4-phenylene group Chemical group [H]C1=C([H])C([*:2])=C([H])C([H])=C1[*:1] 0.000 description 1
- MEKOFIRRDATTAG-UHFFFAOYSA-N 2,2,5,8-tetramethyl-3,4-dihydrochromen-6-ol Chemical compound C1CC(C)(C)OC2=C1C(C)=C(O)C=C2C MEKOFIRRDATTAG-UHFFFAOYSA-N 0.000 description 1
- 101150003085 Pdcl gene Proteins 0.000 description 1
- 238000006069 Suzuki reaction reaction Methods 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- IPWKHHSGDUIRAH-UHFFFAOYSA-N bis(pinacolato)diboron Chemical compound O1C(C)(C)C(C)(C)OB1B1OC(C)(C)C(C)(C)O1 IPWKHHSGDUIRAH-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 150000001649 bromium compounds Chemical class 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- NXQGGXCHGDYOHB-UHFFFAOYSA-L cyclopenta-1,4-dien-1-yl(diphenyl)phosphane;dichloropalladium;iron(2+) Chemical compound [Fe+2].Cl[Pd]Cl.[CH-]1C=CC(P(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1.[CH-]1C=CC(P(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 NXQGGXCHGDYOHB-UHFFFAOYSA-L 0.000 description 1
- NZZFYRREKKOMAT-UHFFFAOYSA-N diiodomethane Chemical compound ICI NZZFYRREKKOMAT-UHFFFAOYSA-N 0.000 description 1
- PBTPREHATAFBEN-UHFFFAOYSA-N dipyrromethane Chemical compound C=1C=CNC=1CC1=CC=CN1 PBTPREHATAFBEN-UHFFFAOYSA-N 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 238000002523 gelfiltration Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 230000009022 nonlinear effect Effects 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 1
- 235000011056 potassium acetate Nutrition 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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Description
この発明は、新規のジポルフィリン誘導体及びポリポルフィリン誘導体に関する。 The present invention relates to novel diporphyrin derivatives and polyporphyrin derivatives.
ポルフィリン類やその金属錯体は、π−共鳴構造を有し、４００ｎｍ前後の吸収帯を有する。このπ−共鳴構造をより大きくすることにより、吸収帯をより長波長側にシフトさせることが可能となる。
ポルフィリン類の金属錯体を用いた反応としては、ポルフィリン類の金属錯体のホウ酸化物付加化物をスズキカップリング反応させる方法が知られている（非特許文献１）。
Porphyrins and metal complexes thereof have a π-resonance structure and have an absorption band around 400 nm. By making this π-resonance structure larger, the absorption band can be shifted to the longer wavelength side.
As a reaction using a metal complex of porphyrins, a method in which a borate adduct of a metal complex of porphyrins is subjected to a Suzuki coupling reaction is known (Non-patent Document 1).
そこで、この発明は、ポルフィリン類の金属錯体より長波長側に吸収帯をシフトされた新規化合物を提供することを目的とする。 Then, this invention aims at providing the novel compound by which the absorption band was shifted to the long wavelength side rather than the metal complex of porphyrins.
この発明は、下記化学式（１）で示される、ジポルフィリン誘導体、下記化学式（３）又は（４）で示される、ポリポルフィリン誘導体、及び下記化学式（５）で示される環状ドデカポルフィリン誘導体を提供することにより、上記課題を解決したのである。
The present invention provides a diporphyrin derivative represented by the following chemical formula (1 ), a polyporphyrin derivative represented by the following chemical formula (3) or (4), and a cyclic dodecaporphyrin derivative represented by the following chemical formula (5). As a result, the above-mentioned problems have been solved.
ポルフィリン類の金属錯体がフェニレン基を介して複数、結合されるので、π−共鳴構造をより大きくすることができ、吸収帯をより長波長側にシフトさせることが可能となる。
そして、得られた化合物は、溶解性を有し、ドナー性、非線形特性（２光子吸収特性）、ホール輸送性等の機能を期待することができ、太陽電池材料、トランジスタ材料、光メモリ材料等への応用が考えられる。
Since a plurality of metal complexes of porphyrins are bonded via a phenylene group, the π-resonance structure can be further increased, and the absorption band can be shifted to the longer wavelength side.
The obtained compound has solubility and can be expected to have functions such as donor property, nonlinear property (two-photon absorption property), hole transport property, and the like, to solar cell materials, transistor materials, optical memory materials, etc. Can be applied.
この発明にかかるジポルフィリン誘導体は、下記化学式（１）で示される１，４−フェニレン架橋ジポルフィリン化合物の亜鉛錯体（以下、「ＺＢ２」と称する。）又は（２）で示される１，３−フェニレン架橋ジポルフィリン化合物の亜鉛錯体（以下、「ＺＡ２」と称する。）である。 The diporphyrin derivative according to the present invention is a 1,3-phenylene-bridged diporphyrin compound zinc complex (hereinafter referred to as “ZB2”) represented by the following chemical formula (1) or 1,3-phenylene represented by (2). A zinc complex of a phenylene-bridged diporphyrin compound (hereinafter referred to as “ZA2”).
なお、上記式（１）又は（２）中、Ａｒは、芳香族炭化水素を表す。また、それぞれのＡｒは同一であっても異なってもよい。上記Ａｒとして好ましい基としては、置換されてもよいフェニルやナフチル基があげられる。この置換基としては、炭素数１〜１５のアルキル基、炭素数１〜１５のアルコキシ基、Ｆ，Ｃｌ，Ｂｒ，Ｉ等のハロゲン等があげられる。 In the above formula (1) or (2), Ar represents an aromatic hydrocarbon. Also, each Ar may be the same or different. Preferred groups as Ar include phenyl and naphthyl groups which may be substituted. Examples of the substituent include an alkyl group having 1 to 15 carbon atoms, an alkoxy group having 1 to 15 carbon atoms, and a halogen such as F, Cl, Br, and I.
上記のＺＢ２やＺＡ２は、ポルフィリン類金属錯体のホウ酸化物付加化合物、例えば、下記化学反応式＜１＞や＜２＞に示される化合物Ｉ（［５−（４’，４’，５’，５’−テトラメチル［１’，３’，２’］ジオキサボロラン−２’−イル）−１０，２０−ジフェニルポルフィナト］亜鉛（ＩＩ））を用い、これに１，４−ジヨードメタン又は１，３−ジヨードメタンを反応させることにより、製造することができる。この反応式は、下記の＜１＞や＜２＞で表すことができる。 ZB2 or ZA2 is a borate addition compound of a porphyrin metal complex, for example, compound I ([5- (4 ′, 4 ′, 5 ′, 5′-tetramethyl [1 ′, 3 ′, 2 ′] dioxaborolan-2′-yl) -10,20-diphenylporfinato] zinc (II)), which is used in 1,4-diiodomethane or 1,3 -It can be produced by reacting diiodomethane. This reaction formula can be represented by the following <1> and <2>.
上記の方法で得られたＺＢ２やＺＡ２は、銀イオン等の金属イオン触媒の存在下で反応することにより、下記の＜３＞や＜４＞に示される反応が生じ、下記化学式（３）で示される１，４−フェニレン架橋ポルフィリン化合物の亜鉛錯体の多量体（以下、「ｎＺＢ２」と称する。）又は（４）で示される１，３−フェニレン架橋ポルフィリン化合物の亜鉛錯体の多量体（以下、「ｎＺＡ２」と称する。）を含むポリポルフィリン誘導体が製造される。更に、ＺＢ２及びＺＡ２を混合して反応させることにより、１，３−フェニレン及び１，４−フェニレン架橋のポリポルフィリン誘導体が製造される。 ZB2 and ZA2 obtained by the above method react in the presence of a metal ion catalyst such as silver ion, thereby causing the reaction shown in the following <3> or <4>. Multimer of zinc complex of 1,4-phenylene bridged porphyrin compound shown below (hereinafter referred to as “nZB2”) or multimer of zinc complex of 1,3-phenylene bridged porphyrin compound shown by (4) A polyporphyrin derivative containing “nZA2”) is produced. Furthermore, by mixing and reacting ZB2 and ZA2, 1,3-phenylene and 1,4-phenylene-crosslinked polyporphyrin derivatives are produced.
なお、上記式（１）〜（４）中のＡｒは、上記と同様のＡｒであり、また、それぞれのＡｒは同一であっても異なってもよい。さらに、ｎは、１〜１０の整数を示す。 Ar in the above formulas (1) to (4) is the same Ar as described above, and each Ar may be the same or different. N represents an integer of 1 to 10.
このようにして得られたｎＺＢ２やｎＺＡ２は、４５０ｎｍ付近に吸収帯を有する。そして、溶解性を有し、ドナー性、非線形特性（２光子吸収特性）、ホール輸送性等の機能を期待することができ、太陽電池材料、トランジスタ材料、光メモリ材料等への応用することができる。 NZB2 and nZA2 obtained in this way have an absorption band near 450 nm. It has solubility and can be expected to have functions such as donor properties, nonlinear characteristics (two-photon absorption characteristics), and hole transport properties, and can be applied to solar cell materials, transistor materials, optical memory materials, and the like. .
特に、ｎＺＡ２のうち、ポルフィリン環を１２個有する下記化合物（６）（以下、「６ＺＡ２」と称する。）は、銀イオン等の上記金属イオン触媒の存在下で反応させると、下記化合物（５）で示される環状ドデカポルフィリン誘導体（以下、「Ｃ６ＺＡ２」と称する。）を製造することができる。このＣ６ＺＡ２は、発光作用を有する。 In particular, among nZA2, the following compound (6) having 12 porphyrin rings (hereinafter referred to as “6ZA2”) is reacted in the presence of the metal ion catalyst such as silver ion, and the following compound (5): A cyclic dodecaporphyrin derivative (hereinafter referred to as “C6ZA2”) can be produced. This C6ZA2 has a light emitting action.
なお、上記式（５），（６）中のＡｒは、上記と同様のＡｒであり、また、それぞれのＡｒは同一であっても異なってもよい。 Ar in the above formulas (5) and (6) is the same Ar as described above, and each Ar may be the same or different.
次に、この発明について、より具体的に実施例を用いて説明する。
（化合物Ｉの製造）
上記化合物Ｉ（［５−（４’，４’，５’，５’−テトラメチル［１’，３’，２’］ジオキサボロラン−２’−イル）−１０，２０−ジ−ｐ−ドデシルオキシフェニルポルフィナト］亜鉛（ＩＩ））を、下記反応式＜５＞に従い、下記の方法で製造した。
Next, the present invention will be described more specifically using examples.
(Production of Compound I)
Compound I ([5- (4 ′, 4 ′, 5 ′, 5′-tetramethyl [1 ′, 3 ′, 2 ′] dioxaborolan-2′-yl) -10,20-di-p-dodecyloxy) [Phenylporfinato] zinc (II)) was produced according to the following reaction formula <5> by the following method.
パラジウム触媒として塩化パラジウム−１，１’−ビス（ジフェニルホスフィノ）フェロセン０．０３ｍｍｏｌ、酢酸カリウム２９４ｍｇ（３．０ｍｍｏｌ）、及び上記反応式＜５＞に示されるジボランのピナコールエステル２７９ｍｇをフラスコに入れ、窒素雰囲気に置換した。
次いで、ジメチルスルホキシド６ｍｌと上記反応式＜５＞に示されるポルフィリン類の臭化物１．０ｍｍｏｌを上記フラスコに加え、８０℃、１０時間撹拌した。反応終了後、ベンゼンで得られた化合物Ｉを抽出した。収率は８０％であった。
As a palladium catalyst, 0.03 mmol of palladium chloride-1,1′-bis (diphenylphosphino) ferrocene, 294 mg (3.0 mmol) of potassium acetate, and 279 mg of diborane pinacol ester represented by the above reaction formula <5> were placed in a flask. And replaced with a nitrogen atmosphere.
Next, 6 ml of dimethyl sulfoxide and 1.0 mmol of bromide of porphyrins represented by the above reaction formula <5> were added to the flask, and the mixture was stirred at 80 ° C. for 10 hours. After completion of the reaction, Compound I obtained with benzene was extracted. The yield was 80%.
得られた化合物ＩのＮＭＲ、ＭＳ及びＵＶのデータは次のとおりである。
・1H NMR (CDCl3, 600 MHz): σ10.30 (s, 1H, meso-H), 9.92 (d, 2H, por-β), 9.40 (d, 2H, por-β), 9.15 (d, 2H, por-β), 9.11 (d, 2H, por-β), 8.13 (d, 4H, Ar), 7.29 (d, 4H, Ar), 4.28 (t, 4H), 2.01 (m, 4H), 1.85 (s, 12H), 1.65 (m, 4H), 1.50-1.30 (broad-m, 32H), and 0.90 (t, 6H).
・MALDI TOF MS found m/z 1019, calcd for C62H79N4O4BZn, m/z 1019;
・UV/Vis (CHCl3); λmax = 414 and 542 nm.
The NMR, MS and UV data of the obtained Compound I are as follows.
・1 H NMR (CDCl 3 , 600 MHz): σ10.30 (s, 1H, meso-H), 9.92 (d, 2H, por-β), 9.40 (d, 2H, por-β), 9.15 (d , 2H, por-β), 9.11 (d, 2H, por-β), 8.13 (d, 4H, Ar), 7.29 (d, 4H, Ar), 4.28 (t, 4H), 2.01 (m, 4H) , 1.85 (s, 12H), 1.65 (m, 4H), 1.50-1.30 (broad-m, 32H), and 0.90 (t, 6H).
MALDI TOF MS found m / z 1019, calcd for C 62 H 79 N 4 O 4 BZn, m / z 1019;
UV / Vis (CHCl 3 ); λ max = 414 and 542 nm.
なお、上記反応式＜５＞に示されるジボランのピナコールエステル（Bis(pinacolate)diboron、正式名称：4,4,4',4',5,5,5',5'-octamethy-2,2'-bi-1,3,2-dioxaborolane）は、アルドリッチ（Ａｌｄｒｉｃｈ）社製の試薬である。 In addition, diborane pinacol ester (Bis (pinacolate) diboron, formal name: 4,4,4 ′, 4 ′, 5,5,5 ′, 5′-octamethy-2,2) represented by the above reaction formula <5> '-bi-1,3,2-dioxaborolane) is a reagent manufactured by Aldrich.
また、上記反応式＜５＞に示されるポルフィリン類の臭化物は、下記の方法で製造される。
まず、１，１０−ジーｐ−ドデシルオキシフェニルーポルフィリンを製造した。すなわち、まず、ｐ−ドデシルオキシフェニルアルデヒド（アルドリッチ社製：試薬）と２，２’−ジピロメタン（アルドリッチ社製：試薬）を１：１で塩化メチレン中に溶解し、トリフルオロ酢酸を約０．６等量加え、室温で２〜３時間ほど撹拌した。次いで、２，３−ジクロロ−５，６−ジシアノ−１，４−ベンゾキノン（アルドリッチ社製：試薬）を約１．６等量加えて、さらに１時間ほど撹拌し、トリエチルアミンで中和後、アルミナカラムを通して濾過した。そして、溶媒を減圧留去してシリカゲルカラムで生成し、塩化メチレン・アセトニトリルで再結晶した。得られた１，１０−ジーｐ−ドデシルオキシフェニルーポルフィリンの収率は、４０％であった。
In addition, bromides of porphyrins represented by the above reaction formula <5> are produced by the following method.
First, 1,10-di-p-dodecyloxyphenyl-porphyrin was produced. That is, first, p-dodecyloxyphenyl aldehyde (manufactured by Aldrich: reagent) and 2,2′-dipyrromethane (manufactured by Aldrich: reagent) are dissolved in methylene chloride at a ratio of 1: 1, and trifluoroacetic acid is dissolved in about 0.000. 6 equivalents was added and stirred at room temperature for 2-3 hours. Next, about 1.6 equivalents of 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (manufactured by Aldrich: reagent) was added, and the mixture was further stirred for about 1 hour, neutralized with triethylamine, and then alumina. Filter through column. Then, the solvent was distilled off under reduced pressure to produce a silica gel column and recrystallized with methylene chloride / acetonitrile. The yield of 1,10-di-p-dodecyloxyphenyl-porphyrin obtained was 40%.
次いで、上記の方法で得られた１，１０−ジーｐ−ドデシルオキシフェニルーポルフィリンをクロロホルムに溶解して、ピリジンを数滴滴下した。溶液を０℃で、ポルフィリンに対して１．５倍当量のＮ−ブロモスクシンイミド（N-bromosuccinimide、関東化学（株）製：試薬）を加え、１時間ほど撹拌した。その後、水にあけてクロロホルムで抽出し、シリカゲルカラムにより目的物を単離した。得られた臭化物の収率は、８０％であった。 Next, 1,10-di-p-dodecyloxyphenyl-porphyrin obtained by the above method was dissolved in chloroform, and several drops of pyridine were added dropwise. At 0 ° C., 1.5-fold equivalent of N-bromosuccinimide (N-bromosuccinimide, manufactured by Kanto Chemical Co., Inc .: reagent) was added to porphyrin, and the mixture was stirred for about 1 hour. Then, it poured in water and extracted with chloroform, and the target object was isolated with the silica gel column. The yield of bromide obtained was 80%.
（ＺＡ２の製造）
上記の方法で得られた化合物Ｉ １４０ｍｇ（０．１３７ｍｍｏｌ）、１，３−ジヨードベンゼン２２．７ｍｇ（０．０６８７ｍｍｏｌ）、Ｃｓ2ＣＯ3１１６ｍｇ、ＰｄＣｌ2（ＰＰｈ3）2１６ｍｇ、ＡｓＰｈ3４．１ｍｇをそれぞれジメチルスルホキシド（ＤＭＦ）に入れて混合した。得られた混合物のガス抜きをして、８０℃で６時間、撹拌した。その後、水洗し、クロロホルムで抽出して、ＭｇＳＯ4で乾燥させ、溶媒を留去した。得られた残渣を、クロロホルム／アセトニトリルで再結晶化させた。そして、ゲルろ過法で分離して、ＺＡ２を分取した。得られたＺＡ２は、７１．７ｍｇ（収率：５６%）であった。
(Manufacture of ZA2)
Compound I 140 mg (0.137 mmol) obtained by the above method, 1,3-diiodobenzene 22.7 mg (0.0687 mmol), Cs 2 CO 3 116 mg, PdCl 2 (PPh 3 ) 2 16 mg, AsPh 3 4 Each 1 mg was mixed in dimethyl sulfoxide (DMF). The resulting mixture was degassed and stirred at 80 ° C. for 6 hours. Thereafter, washing with water, and extracted with chloroform, dried over MgSO 4, and evaporated. The resulting residue was recrystallized from chloroform / acetonitrile. And it isolate | separated with the gel filtration method and fractionated ZA2. The obtained ZA2 was 71.7 mg (yield: 56%).
得られたＺＡ２のＮＭＲ、ＭＳ及びＵＶのデータは次のとおりである。また、吸収スペクトル変化を図１に示す。
・1H NMR (CDCl3, 298K, 600 MHz): σ9.91 (broad, s, 2H, meso-H), 9.41 (d, J= 4.6 Hz, 4H, por-β), 9.17 (d, 4H, por-β), 9.07 (d, 4H, por-β), 9.06 (s, 1H, 1,3-phenylen-H), 8.98 (d,4H, por-β), 8.60 (d,2H, 1,3-phenylen-H), 8.11 (t, J=8.2 Hz, 1H, 1,3-phenylen-H), 8.07(d, 4H, Ar), 7.98(d, 4H, Ar), 7.12(d, 4H, Ar), 7.06 (d, J= 8.3Hz, 4H, Ar), 4.03 (t, 8H), 1.84 (m, 8H), 1.53-1.26 (broad-m, 72H), and 0.90 (t, 12H).
・MALDI-TOF MS found m/z 1861, calcd for C118H138N8O4Zn2, m/z 1863;
・UV/Vis(CHCl3); λmax = 417, 426, 548, and 589 nm.
The NMR, MS and UV data of the obtained ZA2 are as follows. Further, the change in absorption spectrum is shown in FIG.
・1 H NMR (CDCl 3 , 298K, 600 MHz): σ9.91 (broad, s, 2H, meso-H), 9.41 (d, J = 4.6 Hz, 4H, por-β), 9.17 (d, 4H , por-β), 9.07 (d, 4H, por-β), 9.06 (s, 1H, 1,3-phenylen-H), 8.98 (d, 4H, por-β), 8.60 (d, 2H, 1 , 3-phenylen-H), 8.11 (t, J = 8.2 Hz, 1H, 1,3-phenylen-H), 8.07 (d, 4H, Ar), 7.98 (d, 4H, Ar), 7.12 (d, 4H, Ar), 7.06 (d, J = 8.3Hz, 4H, Ar), 4.03 (t, 8H), 1.84 (m, 8H), 1.53-1.26 (broad-m, 72H), and 0.90 (t, 12H ).
MALDI-TOF MS found m / z 1861, calcd for C 118 H 138 N 8 O 4 Zn 2 , m / z 1863;
UV / Vis (CHCl 3 ); λ max = 417, 426, 548, and 589 nm.
（ＺＢ２の製造）
１，３−ジヨードベンゼンのかわりに１，４−ジヨードベンゼンを用いた以外は、上記のＺＡ２の製造方法と同様にして、ＺＢ２を製造した。得られたＺＢ２のＮＭＲ、ＭＳ及びＵＶのデータは次のとおりである。また、吸収スペクトル変化を図２に示す。
・1H NMR (CDCl3, 600 MHz): σ10.25 (s, 2H), 9.44 (d, J=4.6 Hz, 4H), 9.41 (d, J=4.6Hz, 4H), 9.22 (d, J= 4.1Hz, 4H), 9.17 (d, J=4.1Hz, 4H), 8.60 (s, 4H), 8.20 (d, J=8.2Hz, 8H), 7.34 (d, J= 8.3Hz, 8H), 4.30 (t, 8H), 2.02 (m, 8H), 1.66 (m, 8H), 1.50-1.30 (broad-m, 64H), and 0.90 (t, 12H).
・MALDI-TOF MS found m/z 1863, calcd for C118H138N8O4Zn2, m/z 1863;
・UV/Vis(CHCl3); λmax = 420, 425, 548, and 590 nm.
(Production of ZB2)
ZB2 was produced in the same manner as in the production method of ZA2 except that 1,4-diiodobenzene was used instead of 1,3-diiodobenzene. The NMR, MS and UV data of the obtained ZB2 are as follows. Moreover, the absorption spectrum change is shown in FIG.
1 H NMR (CDCl 3 , 600 MHz): σ10.25 (s, 2H), 9.44 (d, J = 4.6 Hz, 4H), 9.41 (d, J = 4.6Hz, 4H), 9.22 (d, J = 4.1Hz, 4H), 9.17 (d, J = 4.1Hz, 4H), 8.60 (s, 4H), 8.20 (d, J = 8.2Hz, 8H), 7.34 (d, J = 8.3Hz, 8H), 4.30 (t, 8H), 2.02 (m, 8H), 1.66 (m, 8H), 1.50-1.30 (broad-m, 64H), and 0.90 (t, 12H).
MALDI-TOF MS found m / z 1863, calcd for C 118 H 138 N 8 O 4 Zn 2 , m / z 1863;
UV / Vis (CHCl 3 ); λ max = 420, 425, 548, and 590 nm.
（ｎＺＡ２、ｎＺＢ２、Ｃ６ＺＡ２の製造）
上記のｎＺＡ２又はｎＺＢ２の１００ｍｇ（０．０５３６ｍｍｏｌ）をクロロホルムに溶解し、０．１ｍｏｌ／ｌのＡｇＰＦ6のアセトニトリル溶液０．５３６ｍｌ（ＡｇＰＦ6含量：０．０５３６ｍｍｏｌ）を加え、室温で6時間、撹拌した。その後、水を加えて希釈し、クロロホルムで抽出した。次いで、乾燥後、Ｚｎ（ＯＡｃ）2でＺｎのメタレーションを行い、ＧＰＣ−ＨＰＬＣで分取した。その結果、２ＺＡ２、３ＺＡ２、４ＺＡ２、６ＺＡ２、Ｃ６ＺＡ２、２ＺＢ２、３ＺＢ２、４ＺＢ２、６ＺＢ２、８ＺＢ２、１２ＺＢ２、１６ＺＢ２等が得られた。以下に、得られたｎＺＢ２のＮＭＲ、ＭＳ及びＵＶのデータを示す。また、吸収スペクトル変化を図１又は２に示す。
(Manufacture of nZA2, nZB2, C6ZA2)
100 mg (0.0536 mmol) of the above-mentioned nZA2 or nZB2 was dissolved in chloroform, 0.536 ml of 0.1 mol / l AgPF 6 acetonitrile solution (AgPF 6 content: 0.0536 mmol) was added, and the mixture was stirred at room temperature for 6 hours. did. Then, it diluted by adding water and extracted with chloroform. Subsequently, after drying, Zn metallation was performed with Zn (OAc) 2 and fractionated by GPC-HPLC. As a result, 2ZA2, 3ZA2, 4ZA2, 6ZA2, C6ZA2, 2ZB2, 3ZB2, 4ZB2, 6ZB2, 8ZB2, 12ZB2, 16ZB2, and the like were obtained. The NMR, MS and UV data of the obtained nZB2 are shown below. The change in absorption spectrum is shown in FIG.
［２ＺＡ２］
・1H NMR (CDCl3, 298K, 600 MHz): σ10.06 (broad, s, 2H, meso-H), 9.51 (m, 8H, por-β), 9.28 (d, 4H, por-β), 9.14-9.21 (m, 10H, (8H,por-β; 2H, 1,3-phenylen-H)), 9.07 (d, 4H, por-β), 8.62-8.73 (m, 8H, (4H, por-β; 4H, 1, 3-phenylen-H)), 7.99-8.16 (m, 22H, (16H Ar; 4H, por-β; 2H, 1,3-phenylen-H)), 7.03-7.18 (m, 16H, Ar), 4.04-4.15 (m, 16H), 1.80-1.94 (m, 16H), 1.22-1.60 (broad-m, 144H), and 0.80-0.90 (m, 24H).
・MALDI-TOF MS found m/z 3719, calcd for C236H274N16O8Zn4, m/z 3724;
・UV/Vis(CHCl3); λmax = 418, 465, 554, and 608 nm.
[2ZA2]
・1 H NMR (CDCl 3 , 298K, 600 MHz): σ10.06 (broad, s, 2H, meso-H), 9.51 (m, 8H, por-β), 9.28 (d, 4H, por-β) , 9.14-9.21 (m, 10H, (8H, por-β; 2H, 1,3-phenylen-H)), 9.07 (d, 4H, por-β), 8.62-8.73 (m, 8H, (4H, por-β; 4H, 1, 3-phenylen-H)), 7.99-8.16 (m, 22H, (16H Ar; 4H, por-β; 2H, 1,3-phenylen-H)), 7.03-7.18 ( m, 16H, Ar), 4.04-4.15 (m, 16H), 1.80-1.94 (m, 16H), 1.22-1.60 (broad-m, 144H), and 0.80-0.90 (m, 24H).
MALDI-TOF MS found m / z 3719, calcd for C 236 H 274 N 16 O 8 Zn 4 , m / z 3724;
UV / Vis (CHCl 3 ); λ max = 418, 465, 554, and 608 nm.
［３ＺＡ２］
・1H NMR (CDCl3, 298K, 600 MHz): σ10.13 (s, 2H, meso-H), 9.51-9.56 (m, 12H, por-β), 9.30 (d, 4H, por-β), 9.14-9.21 (m, 15H, (12H,por-β; 3H, 1,3-phenylen-H)), 9.10 (d, 4H, por-β), 8.64-8.76 (m, 14H, (8H, por-β; 6H, 1,3-phenylen-H)), 7.99-8.24 (m, 35H, (24H Ar; 8H, por-(; 3H, 1,3-phenylen-H)), 7.03-7.28 (m, 24H, Ar), 4.09-4.19 (m, 24H), 1.84-1.96 (m, 24H), 1.25-1.62 (broad-m, 216H), and 0.80-0.90 (m, 36H).
・MALDI-TOF MS found m/z 5590, calcd for C354H410N24O12Zn6, m/z 5585;
・UV/Vis(CHCl3); λmax = 419, 470, 566, and 610 nm.
[3ZA2]
・1 H NMR (CDCl 3 , 298K, 600 MHz): σ10.13 (s, 2H, meso-H), 9.51-9.56 (m, 12H, por-β), 9.30 (d, 4H, por-β) , 9.14-9.21 (m, 15H, (12H, por-β; 3H, 1,3-phenylen-H)), 9.10 (d, 4H, por-β), 8.64-8.76 (m, 14H, (8H, por-β; 6H, 1,3-phenylen-H)), 7.99-8.24 (m, 35H, (24H Ar; 8H, por- (; 3H, 1,3-phenylen-H))), 7.03-7.28 ( m, 24H, Ar), 4.09-4.19 (m, 24H), 1.84-1.96 (m, 24H), 1.25-1.62 (broad-m, 216H), and 0.80-0.90 (m, 36H).
MALDI-TOF MS found m / z 5590, calcd for C 354 H 410 N 24 O 12 Zn 6 , m / z 5585;
UV / Vis (CHCl 3 ); λ max = 419, 470, 566, and 610 nm.
［４ＺＡ２］
・1H NMR (CDCl3, 298K, 600 MHz): σ10.21 (s, 2H, meso-H), 9.50-9.55 (m, 16H, por-β), 9.37 (d, 4H, por-β), 9.14-9.30 (m, 24H, (20H,por-β; 4H, 1,3-phenylen-H)), 8.63-8.76 (m, 20H, (12H, por-β; 8H, 1,3-phenylen-H)), 8.00-8.24 (m, 48H, (32H Ar; 12H, por-β; 4H, 1, 3-phenylen-H)), 7.10-7.32 (m, 32H, Ar), 4.10-4.23 (m, 32H), 1.85-2.00 (m, 32H), 1.20-1.56 (broad-m, 288H), and 0.80-0.90 (t, 48H).
・MALDI-TOF MS found m/z 7483, calcd for C472H546N32O16Zn8, m/z 7447;
・UV/Vis(CHCl3); λmax = 419, 471, 566, and 610 nm.
[4ZA2]
・1 H NMR (CDCl 3 , 298K, 600 MHz): σ10.21 (s, 2H, meso-H), 9.50-9.55 (m, 16H, por-β), 9.37 (d, 4H, por-β) , 9.14-9.30 (m, 24H, (20H, por-β; 4H, 1,3-phenylen-H)), 8.63-8.76 (m, 20H, (12H, por-β; 8H, 1,3-phenylen -H)), 8.00-8.24 (m, 48H, (32H Ar; 12H, por-β; 4H, 1, 3-phenylen-H)), 7.10-7.32 (m, 32H, Ar), 4.10-4.23 ( m, 32H), 1.85-2.00 (m, 32H), 1.20-1.56 (broad-m, 288H), and 0.80-0.90 (t, 48H).
MALDI-TOF MS found m / z 7483, calcd for C 472 H 546 N 32 O 16 Zn 8 , m / z 7447;
UV / Vis (CHCl 3 ); λ max = 419, 471, 566, and 610 nm.
［６ＺＡ２］
・1H NMR (CDCl3, 298K, 600 MHz): σ 10.24 (s, 2H, meso-H), 9.48-9.54 (m, 24H, por-β), 9.39 (d, 4H, por-β), 9.14-9.28 (m, 34H, (28H,por-β; 6H, 1, 3-phenylen-H)), 8.64-8.72 (m, 32H, (20H, por-β; 12H, 1,3-phenylen-H)), 8.00-8.20 (m, 74H, (48H Ar; 20H, por-β; 6H, 1,3-phenylen-H)), 7.07-7.33 (m, 48H, Ar), 4.12-4.27 (m, 48H), 1.86-2.01 (m, 48H), 1.21-1.58 (broad-m, 432H), and 0.80-0.90 (m, 72H).
・MALDI-TOF MS found m/z 11169, calcd for C708H818N48O24Zn12, m/z 11169;
・UV/Vis(CHCl3), λmax = 419, 472, 566, and 610 nm
[6ZA2]
・1 H NMR (CDCl 3 , 298K, 600 MHz): σ 10.24 (s, 2H, meso-H), 9.48-9.54 (m, 24H, por-β), 9.39 (d, 4H, por-β), 9.14-9.28 (m, 34H, (28H, por-β; 6H, 1, 3-phenylen-H)), 8.64-8.72 (m, 32H, (20H, por-β; 12H, 1,3-phenylen- H)), 8.00-8.20 (m, 74H, (48H Ar; 20H, por-β; 6H, 1,3-phenylen-H)), 7.07-7.33 (m, 48H, Ar), 4.12-4.27 (m , 48H), 1.86-2.01 (m, 48H), 1.21-1.58 (broad-m, 432H), and 0.80-0.90 (m, 72H).
MALDI-TOF MS found m / z 11169, calcd for C 708 H 818 N 48 O 24 Zn 12 , m / z 11169;
UV / Vis (CHCl 3 ), λ max = 419, 472, 566, and 610 nm
［Ｃ６ＺＡ２］
・1H NMR (CDCl3, 298K, 600 MHz): σ9.522 (d, J=4.08Hz, 12H, Por-β) 9.482 (d, J=4.62 Hz, 12H, Por-β), 9.185 (d, J=4.68 Hz, 12H, Por-β), 9.146 (d, J=4.56 Hz, 12H, Por-β), 8.904 (s, 6H, Phenyl), 8.879 (d, J=7.8Hz, 12H, Phenyl), 8.784 (d, J=4.14 Hz, 12H, Por-β), 8.500 (d, J=5.04 Hz, 12H, Por-β), 8.398 (d, J=4.56 Hz, 12H, Por-β), 8.296 (t, J=14.64 Hz, 6H, Phenyl), 8.159-8.137 (m, 24H, Ar) 8.045 (d, J=7.8 Hz, 12H, Ar), 7.986 (d, J=8.28Hz, 12H, Ar), 7.705 (d, J=5.04 Hz, 12H, Por-β), 7.258-7.200 (m, 24H, Ar), 7.128 (d, J=8.54Hz, 12H, Ar), 7.060 (d, J=8.76 Hz, 12H, Ar,), 4.203 (broad, 24H), 4.067 (broad, 24H), 1.952-1.1.920 (m, 24H), 1.824-1.788 (b, 24H), 1.610-1.148 (m, 432H), 0.867 (t, J=13.2 Hz, 36H), 0.730 (t, J=12.8 Hz, 36H)
・MALDI-TOF MS found m/z 11167, calcd for C708H816N48O24Zn12, m/z 11167;
・UV/Vis(CHCl3), λmax = 420, 472, 567, and 610 nm.
[C6ZA2]
1 H NMR (CDCl 3 , 298K, 600 MHz): σ9.522 (d, J = 4.08Hz, 12H, Por-β) 9.482 (d, J = 4.62 Hz, 12H, Por-β), 9.185 (d , J = 4.68 Hz, 12H, Por-β), 9.146 (d, J = 4.56 Hz, 12H, Por-β), 8.904 (s, 6H, Phenyl), 8.879 (d, J = 7.8Hz, 12H, Phenyl ), 8.784 (d, J = 4.14 Hz, 12H, Por-β), 8.500 (d, J = 5.04 Hz, 12H, Por-β), 8.398 (d, J = 4.56 Hz, 12H, Por-β), 8.296 (t, J = 14.64 Hz, 6H, Phenyl), 8.159-8.137 (m, 24H, Ar) 8.045 (d, J = 7.8 Hz, 12H, Ar), 7.986 (d, J = 8.28Hz, 12H, Ar ), 7.705 (d, J = 5.04 Hz, 12H, Por-β), 7.258-7.200 (m, 24H, Ar), 7.128 (d, J = 8.54Hz, 12H, Ar), 7.060 (d, J = 8.76 Hz, 12H, Ar,), 4.203 (broad, 24H), 4.067 (broad, 24H), 1.952-1.1.920 (m, 24H), 1.824-1.788 (b, 24H), 1.610-1.148 (m, 432H) , 0.867 (t, J = 13.2 Hz, 36H), 0.730 (t, J = 12.8 Hz, 36H)
MALDI-TOF MS found m / z 11167, calcd for C 708 H 816 N 48 O 24 Zn 12 , m / z 11167;
UV / Vis (CHCl 3 ), λ max = 420, 472, 567, and 610 nm.
［２ＺＢ２］
・1H NMR (CDCl3, 600 MHz): σ 10.22 (s, 2H), 9.52 (m, 8H), 9.41 (d, J=4.6Hz, 4H), 9.39 (d, J=4.6Hz, 4H), 9.27 (m, 8H), 9.17 (d, J=4.1Hz, 4H), 8.80 (d, J=5.0Hz, 4H), 8.71 (d, J=7.3Hz, 4H), 8.68 (d, J=7.3Hz, 4H), 8.21 (m, 20H), 7.34 (d, J=8.8Hz, 8H), 7.23 (d, J=8.8Hz, 8H), 4.28 (t, 8H), 4.17 (t, 8H), 2.01 (m, 8H), 1.91 (m, 8H), 1.60-1.26 (broad-m, 144H), 0.90 (t, 12H), and 0.84 (t, 12H).
・MALDI-TOF MS found m/z 3721, calcd for C236H274N16O8Zn4, m/z 3724;
・UV/Vis(CHCl3); λmax = 420, 465, 555, and 609 nm.
[2ZB2]
・1 H NMR (CDCl 3 , 600 MHz): σ 10.22 (s, 2H), 9.52 (m, 8H), 9.41 (d, J = 4.6Hz, 4H), 9.39 (d, J = 4.6Hz, 4H) , 9.27 (m, 8H), 9.17 (d, J = 4.1Hz, 4H), 8.80 (d, J = 5.0Hz, 4H), 8.71 (d, J = 7.3Hz, 4H), 8.68 (d, J = 7.3Hz, 4H), 8.21 (m, 20H), 7.34 (d, J = 8.8Hz, 8H), 7.23 (d, J = 8.8Hz, 8H), 4.28 (t, 8H), 4.17 (t, 8H) , 2.01 (m, 8H), 1.91 (m, 8H), 1.60-1.26 (broad-m, 144H), 0.90 (t, 12H), and 0.84 (t, 12H).
MALDI-TOF MS found m / z 3721, calcd for C 236 H 274 N 16 O 8 Zn 4 , m / z 3724;
UV / Vis (CHCl 3 ); λ max = 420, 465, 555, and 609 nm.
［３ＺＢ２］
・1H NMR (CDCl3, 600 MHz): σ10.28 (s, 2H), 9.51-9.58 (m, 12H), 9.44 (d, J=4.6Hz, 4H), 9.30-9.26 (m, 12H), 9.20 (d, J=4.14Hz, 4H), 8.79-8.81 (m, 12H), 8.73-8.68 (m, 8H), 8.22-8.25 (m, 32H), 7.36 (d, J=8.8 Hz, 8H), 7.7.25-7.27 (m, 16H), 4.29 (t, 8H), 4.20 (m, 16H),2.03 (m, 8H), 1.93 (m, 16H), 1.70-1.26 (broad-m, 216H), 0.91 (t, 12H), and 0.84 (m, 24H).
・MALDI-TOF MS found m/z 5579, calcd for C354H410N24O12Zn6, m/z 5586;
・UV/Vis(CHCl3); λmax = 420, 471, 566, and 612 nm.
[3ZB2]
・1 H NMR (CDCl 3 , 600 MHz): σ10.28 (s, 2H), 9.51-9.58 (m, 12H), 9.44 (d, J = 4.6Hz, 4H), 9.30-9.26 (m, 12H) , 9.20 (d, J = 4.14Hz, 4H), 8.79-8.81 (m, 12H), 8.73-8.68 (m, 8H), 8.22-8.25 (m, 32H), 7.36 (d, J = 8.8 Hz, 8H ), 7.7.25-7.27 (m, 16H), 4.29 (t, 8H), 4.20 (m, 16H), 2.03 (m, 8H), 1.93 (m, 16H), 1.70-1.26 (broad-m, 216H ), 0.91 (t, 12H), and 0.84 (m, 24H).
MALDI-TOF MS found m / z 5579, calcd for C 354 H 410 N 24 O 12 Zn 6 , m / z 5586;
UV / Vis (CHCl 3 ); λ max = 420, 471, 566, and 612 nm.
［４ＺＢ２］
・1H NMR (CDCl3, 600 MHz): σ10.31 (s, 2H), 9.58-9.46(m, 20H), 9.29-9.21 (m, 20H), 8.82-8.72 (m, 28H), 8.26-8.21 (m, 44H), 7.37 (d, J=8.8Hz, 8H), 7.27 (m, 24H), 4.32 (t, 8H), 4.22 (m, 24H), 2.04 (m, 8H), 1.94 (m, 24H), 1.60-1.26 (broad-m, 288H), 0.91 (t, 12H) 0.84-0.90 (m, 48H).
・MALDI-TOF MS found m/z 7442, calcd for C472H546N32O16Zn8, m/z 7447;
・UV/Vis(CHCl3); λmax = 420, 474, 568, and 612 nm.
[4ZB2]
・1 H NMR (CDCl 3 , 600 MHz): σ10.31 (s, 2H), 9.58-9.46 (m, 20H), 9.29-9.21 (m, 20H), 8.82-8.72 (m, 28H), 8.26- 8.21 (m, 44H), 7.37 (d, J = 8.8Hz, 8H), 7.27 (m, 24H), 4.32 (t, 8H), 4.22 (m, 24H), 2.04 (m, 8H), 1.94 (m , 24H), 1.60-1.26 (broad-m, 288H), 0.91 (t, 12H) 0.84-0.90 (m, 48H).
MALDI-TOF MS found m / z 7442, calcd for C 472 H 546 N 32 O 16 Zn 8 , m / z 7447;
UV / Vis (CHCl 3 ); λ max = 420, 474, 568, and 612 nm.
［６ＺＢ２］
・1H NMR (CDCl3, 600 MHz): σ10.30 (s, 2H), 9.56-9.45(m, 28H), 9.28-9.21 (m, 28H), 8.79-8.67 (m, 44H), 8.25-8.16 (m, 68H), 7.36 (d, J=8.8Hz, 8H), 7.26-7.29 (m, 40H), 4.32 (t, 8H), 4.22 (m, 40H), 2.05 (m, 8H), 1.94 (m, 40H), 1.60-1.26 (broad-m, 432H), 0.84-0.92 (m, 72H).
・MALDI-TOF MS found m/z 11241, calcd for C708H818N48O24Zn12, m/z 11169;
・UV/Vis(CHCl3); λmax = 420, 475, 568, and 612 nm.
[6ZB2]
・1 H NMR (CDCl 3 , 600 MHz): σ10.30 (s, 2H), 9.56-9.45 (m, 28H), 9.28-9.21 (m, 28H), 8.79-8.67 (m, 44H), 8.25- 8.16 (m, 68H), 7.36 (d, J = 8.8Hz, 8H), 7.26-7.29 (m, 40H), 4.32 (t, 8H), 4.22 (m, 40H), 2.05 (m, 8H), 1.94 (m, 40H), 1.60-1.26 (broad-m, 432H), 0.84-0.92 (m, 72H).
MALDI-TOF MS found m / z 11241, calcd for C 708 H 818 N 48 O 24 Zn 12 , m / z 11169;
UV / Vis (CHCl 3 ); λ max = 420, 475, 568, and 612 nm.
［８ＺＢ２］
・1H NMR (CDCl3, 600 MHz): σ10.32 (s, 2H), 9.58-9.47(m, 36H), 9.30-9.22 (m, 36H), 8.82-8.67 (m, 60H), 8.25-8.16 (m, 92H), 7.36 (d, J=8.8Hz, 8H), 7.25-7.29 (m, 56H), 4.32-4.20 (m, 64H), 2.05-1.94 (m, 64H), 1.60-1.26 (broad-m, 576H), 0.84-0.92 (m, 96H).
・MALDI-TOF MS found m/z 15121, calcd for C944H1090N64O32Zn16, m/z 14891;
・UV/Vis(CHCl3); λmax = 420, 476, 568, and 612 nm.
[8ZB2]
・1 H NMR (CDCl 3 , 600 MHz): σ10.32 (s, 2H), 9.58-9.47 (m, 36H), 9.30-9.22 (m, 36H), 8.82-8.67 (m, 60H), 8.25- 8.16 (m, 92H), 7.36 (d, J = 8.8Hz, 8H), 7.25-7.29 (m, 56H), 4.32-4.20 (m, 64H), 2.05-1.94 (m, 64H), 1.60-1.26 ( broad-m, 576H), 0.84-0.92 (m, 96H).
MALDI-TOF MS found m / z 15121, calcd for C 944 H 1090 N 64 O 32 Zn 16 , m / z 14891;
UV / Vis (CHCl 3 ); λ max = 420, 476, 568, and 612 nm.
［１２ＺＢ２］
・1H NMR (CDCl3, 600 MHz): σ10.32 (s, 2H), 9.56-9.46(m, 52H), 9.29-9.21 (m, 52H), 8.81-8.66 (m, 92H), 8.25-8.17 (m, 140H), 7.36-7.25 (m, 96H), 4.32-4.20 (m, 96H), 2.05-1.94 (m, 96H), 1.60-1.26 (broad-m, 864H), 0.84-0.92 (m, 144H).
・MALDI-TOF MS found m/z 22616; calcd for C1416H1634N96O48Zn24, m/z 22336;
・UV/Vis(CHCl3); λmax = 420, 476, 568, and 613 nm
[12ZB2]
・1 H NMR (CDCl 3 , 600 MHz): σ10.32 (s, 2H), 9.56-9.46 (m, 52H), 9.29-9.21 (m, 52H), 8.81-8.66 (m, 92H), 8.25- 8.17 (m, 140H), 7.36-7.25 (m, 96H), 4.32-4.20 (m, 96H), 2.05-1.94 (m, 96H), 1.60-1.26 (broad-m, 864H), 0.84-0.92 (m , 144H).
MALDI-TOF MS found m / z 22616; calcd for C 1416 H 1634 N 96 O 48 Zn 24 , m / z 22336;
UV / Vis (CHCl 3 ); λ max = 420, 476, 568, and 613 nm
［１６ＺＢ２］
・1H NMR (CDCl3, 600 MHz): σ10.31 (s, 2H), 9.56-9.46(m, 68H), 9.29-9.21 (m, 68H), 8.81-8.66 (m, 124H), 8.25-8.17 (m, 188H), 7.36-7.25 (m, 128H), 4.32-4.20 (m, 128H), 2.05-1.94 (m, 128H), 1.60-1.26 (broad-m, 1152H), 0.84-0.92 (m, 192H).
・UV/Vis(CHCl3); λmax = 420, 476, 568, and 613 nm
[16ZB2]
・1 H NMR (CDCl 3 , 600 MHz): σ10.31 (s, 2H), 9.56-9.46 (m, 68H), 9.29-9.21 (m, 68H), 8.81-8.66 (m, 124H), 8.25- 8.17 (m, 188H), 7.36-7.25 (m, 128H), 4.32-4.20 (m, 128H), 2.05-1.94 (m, 128H), 1.60-1.26 (broad-m, 1152H), 0.84-0.92 (m , 192H).
UV / Vis (CHCl 3 ); λ max = 420, 476, 568, and 613 nm
（Ｃ６ＺＡ２の製造）
上記の６ＺＡ２の１００ｍｇ（０．０５３６ｍｍｏｌ）をクロロホルムに溶解し、０．１ｍｏｌ／ｌのＡｇＰＦ6のアセトニトリル溶液０．５３６ｍｌ（ＡｇＰＦ6含量：０．０５３６ｍｍｏｌ）を加え、室温で6時間、撹拌した。その後、水を加えて希釈し、クロロホルムで抽出した。次いで、乾燥後、Ｚｎ（ＯＡｃ）2でＺｎのメタレーションを行った。その結果、Ｃ６ＺＡ２が得られているのを確認した。
(Manufacture of C6ZA2)
100 mg (0.0536 mmol) of the above 6ZA2 was dissolved in chloroform, 0.536 ml (AgPF 6 content: 0.0536 mmol) of 0.1 mol / l AgPF 6 in acetonitrile was added, and the mixture was stirred at room temperature for 6 hours. Then, it diluted by adding water and extracted with chloroform. Next, after drying, Zn metallation was performed with Zn (OAc) 2 . As a result, it was confirmed that C6ZA2 was obtained.
Claims (4)
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