JP6833188B2 - Compounds, light emitting or electronic materials using them, and gas sensor materials - Google Patents
Compounds, light emitting or electronic materials using them, and gas sensor materials Download PDFInfo
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- 150000001875 compounds Chemical class 0.000 title claims description 78
- 239000000463 material Substances 0.000 title claims description 39
- 239000012776 electronic material Substances 0.000 title claims description 8
- 239000007789 gas Substances 0.000 claims description 55
- 125000004432 carbon atom Chemical group C* 0.000 claims description 43
- 125000000217 alkyl group Chemical group 0.000 claims description 35
- 230000015572 biosynthetic process Effects 0.000 claims description 30
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 22
- 239000002253 acid Substances 0.000 claims description 22
- 229910052757 nitrogen Inorganic materials 0.000 claims description 19
- 229910052799 carbon Inorganic materials 0.000 claims description 13
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 11
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 10
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 claims description 10
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 9
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 claims description 9
- 125000003368 amide group Chemical group 0.000 claims description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 8
- 125000004076 pyridyl group Chemical group 0.000 claims description 8
- 150000001721 carbon Chemical group 0.000 claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 claims description 5
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- 239000011574 phosphorus Substances 0.000 claims description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 45
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- 238000006243 chemical reaction Methods 0.000 description 31
- 239000000243 solution Substances 0.000 description 28
- 238000003786 synthesis reaction Methods 0.000 description 28
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 27
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 23
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 20
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 20
- 239000002904 solvent Substances 0.000 description 20
- 239000007788 liquid Substances 0.000 description 18
- 239000000203 mixture Substances 0.000 description 18
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- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 14
- 239000010409 thin film Substances 0.000 description 14
- 230000002378 acidificating effect Effects 0.000 description 13
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- 125000005677 ethinylene group Chemical group [*:2]C#C[*:1] 0.000 description 13
- 238000000746 purification Methods 0.000 description 13
- 238000002189 fluorescence spectrum Methods 0.000 description 11
- 238000002844 melting Methods 0.000 description 11
- 230000008018 melting Effects 0.000 description 11
- 238000003756 stirring Methods 0.000 description 11
- 229910021595 Copper(I) iodide Inorganic materials 0.000 description 10
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 9
- -1 p-phenylene ethynylenes Chemical class 0.000 description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- FPGGTKZVZWFYPV-UHFFFAOYSA-M tetrabutylammonium fluoride Chemical compound [F-].CCCC[N+](CCCC)(CCCC)CCCC FPGGTKZVZWFYPV-UHFFFAOYSA-M 0.000 description 8
- 238000010521 absorption reaction Methods 0.000 description 7
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 7
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical group C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 6
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- 239000004065 semiconductor Substances 0.000 description 5
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- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- UEXCJVNBTNXOEH-UHFFFAOYSA-N Ethynylbenzene Chemical compound C#CC1=CC=CC=C1 UEXCJVNBTNXOEH-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 230000031700 light absorption Effects 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- 125000000714 pyrimidinyl group Chemical group 0.000 description 4
- 238000001338 self-assembly Methods 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 125000001424 substituent group Chemical group 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- UDGKZGLPXCRRAM-UHFFFAOYSA-N 1,2,5-thiadiazole Chemical group C=1C=NSN=1 UDGKZGLPXCRRAM-UHFFFAOYSA-N 0.000 description 3
- BBOLNFYSRZVALD-UHFFFAOYSA-N 1,2-diiodobenzene Chemical compound IC1=CC=CC=C1I BBOLNFYSRZVALD-UHFFFAOYSA-N 0.000 description 3
- PDQRQJVPEFGVRK-UHFFFAOYSA-N 2,1,3-benzothiadiazole Chemical group C1=CC=CC2=NSN=C21 PDQRQJVPEFGVRK-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical group C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 125000002723 alicyclic group Chemical group 0.000 description 3
- 239000004020 conductor Substances 0.000 description 3
- YNHIGQDRGKUECZ-UHFFFAOYSA-N dichloropalladium;triphenylphosphanium Chemical compound Cl[Pd]Cl.C1=CC=CC=C1[PH+](C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1[PH+](C=1C=CC=CC=1)C1=CC=CC=C1 YNHIGQDRGKUECZ-UHFFFAOYSA-N 0.000 description 3
- 239000010408 film Substances 0.000 description 3
- 125000005842 heteroatom Chemical group 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 3
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 3
- CWMFRHBXRUITQE-UHFFFAOYSA-N trimethylsilylacetylene Chemical group C[Si](C)(C)C#C CWMFRHBXRUITQE-UHFFFAOYSA-N 0.000 description 3
- GHYOCDFICYLMRF-UTIIJYGPSA-N (2S,3R)-N-[(2S)-3-(cyclopenten-1-yl)-1-[(2R)-2-methyloxiran-2-yl]-1-oxopropan-2-yl]-3-hydroxy-3-(4-methoxyphenyl)-2-[[(2S)-2-[(2-morpholin-4-ylacetyl)amino]propanoyl]amino]propanamide Chemical compound C1(=CCCC1)C[C@@H](C(=O)[C@@]1(OC1)C)NC([C@H]([C@@H](C1=CC=C(C=C1)OC)O)NC([C@H](C)NC(CN1CCOCC1)=O)=O)=O GHYOCDFICYLMRF-UTIIJYGPSA-N 0.000 description 2
- QFLWZFQWSBQYPS-AWRAUJHKSA-N (3S)-3-[[(2S)-2-[[(2S)-2-[5-[(3aS,6aR)-2-oxo-1,3,3a,4,6,6a-hexahydrothieno[3,4-d]imidazol-4-yl]pentanoylamino]-3-methylbutanoyl]amino]-3-(4-hydroxyphenyl)propanoyl]amino]-4-[1-bis(4-chlorophenoxy)phosphorylbutylamino]-4-oxobutanoic acid Chemical compound CCCC(NC(=O)[C@H](CC(O)=O)NC(=O)[C@H](Cc1ccc(O)cc1)NC(=O)[C@@H](NC(=O)CCCCC1SC[C@@H]2NC(=O)N[C@H]12)C(C)C)P(=O)(Oc1ccc(Cl)cc1)Oc1ccc(Cl)cc1 QFLWZFQWSBQYPS-AWRAUJHKSA-N 0.000 description 2
- UNILWMWFPHPYOR-KXEYIPSPSA-M 1-[6-[2-[3-[3-[3-[2-[2-[3-[[2-[2-[[(2r)-1-[[2-[[(2r)-1-[3-[2-[2-[3-[[2-(2-amino-2-oxoethoxy)acetyl]amino]propoxy]ethoxy]ethoxy]propylamino]-3-hydroxy-1-oxopropan-2-yl]amino]-2-oxoethyl]amino]-3-[(2r)-2,3-di(hexadecanoyloxy)propyl]sulfanyl-1-oxopropan-2-yl Chemical compound O=C1C(SCCC(=O)NCCCOCCOCCOCCCNC(=O)COCC(=O)N[C@@H](CSC[C@@H](COC(=O)CCCCCCCCCCCCCCC)OC(=O)CCCCCCCCCCCCCCC)C(=O)NCC(=O)N[C@H](CO)C(=O)NCCCOCCOCCOCCCNC(=O)COCC(N)=O)CC(=O)N1CCNC(=O)CCCCCN\1C2=CC=C(S([O-])(=O)=O)C=C2CC/1=C/C=C/C=C/C1=[N+](CC)C2=CC=C(S([O-])(=O)=O)C=C2C1 UNILWMWFPHPYOR-KXEYIPSPSA-M 0.000 description 2
- YHWFCFIXXMXRBF-UHFFFAOYSA-N 2,5-diiodopyridine Chemical compound IC1=CC=C(I)N=C1 YHWFCFIXXMXRBF-UHFFFAOYSA-N 0.000 description 2
- LGZJJXVWGCAGKB-UHFFFAOYSA-N 7-(chloromethyl)pentadecane Chemical compound CCCCCCCCC(CCl)CCCCCC LGZJJXVWGCAGKB-UHFFFAOYSA-N 0.000 description 2
- YNHIGQDRGKUECZ-UHFFFAOYSA-L PdCl2(PPh3)2 Substances [Cl-].[Cl-].[Pd+2].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 YNHIGQDRGKUECZ-UHFFFAOYSA-L 0.000 description 2
- 238000003477 Sonogashira cross-coupling reaction Methods 0.000 description 2
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- 229910021529 ammonia Inorganic materials 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 229940125797 compound 12 Drugs 0.000 description 2
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- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- QENHCSSJTJWZAL-UHFFFAOYSA-N magnesium sulfide Chemical compound [Mg+2].[S-2] QENHCSSJTJWZAL-UHFFFAOYSA-N 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 230000003595 spectral effect Effects 0.000 description 2
- CBYDUPRWILCUIC-UHFFFAOYSA-N 1,2-diethynylbenzene Chemical compound C#CC1=CC=CC=C1C#C CBYDUPRWILCUIC-UHFFFAOYSA-N 0.000 description 1
- MVLGANVFCMOJHR-UHFFFAOYSA-N 1,4-diethynylbenzene Chemical compound C#CC1=CC=C(C#C)C=C1 MVLGANVFCMOJHR-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
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- AQWGOTHUVVKPTG-UHFFFAOYSA-N 2,3-diiodopyridine Chemical compound IC1=CC=CN=C1I AQWGOTHUVVKPTG-UHFFFAOYSA-N 0.000 description 1
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- XVMSFILGAMDHEY-UHFFFAOYSA-N 6-(4-aminophenyl)sulfonylpyridin-3-amine Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=N1 XVMSFILGAMDHEY-UHFFFAOYSA-N 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
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- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
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- KAKZBPTYRLMSJV-UHFFFAOYSA-N butadiene group Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
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- IXCSERBJSXMMFS-UHFFFAOYSA-N hcl hcl Chemical compound Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
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Landscapes
- Pyridine Compounds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Investigating Or Analysing Materials By The Use Of Chemical Reactions (AREA)
- Nitrogen- Or Sulfur-Containing Heterocyclic Ring Compounds With Rings Of Six Or More Members (AREA)
Description
本発明は、化合物、それを用いた発光若しくは電子材料、及びガスセンサ材料に関する。 The present invention relates to a compound, a light emitting or electronic material using the compound, and a gas sensor material.
π共役オリゴマーは、二重結合や三重結合といった多重結合と単結合とを繰り返し持つ化合物の総称であり、古くから色素材料として用いられてきた他、最近ではその高い発光特性や電気伝導性を活かして、有機発光デバイスやナノデバイス等の材料として応用されている。このような応用例として、例えば特許文献１には、高分子有機半導体を形成するのに有用なπ共役高分子として、芳香環とブタジエン骨格とが互い違いに結合して主鎖を構成する化合物が提案されている。 π-conjugated oligomer is a general term for compounds that repeatedly have multiple bonds and single bonds such as double bonds and triple bonds. It has been used as a dye material for a long time, and recently, it takes advantage of its high light emission characteristics and electrical conductivity. It is applied as a material for organic light emitting devices and nanodevices. As an example of such an application, for example, Patent Document 1 describes a compound in which an aromatic ring and a butadiene skeleton are alternately bonded to form a main chain as a π-conjugated polymer useful for forming a polymer organic semiconductor. Proposed.
このようなπ共役オリゴマーの一つとして、ｐ−フェニレン基とエチニレン基とが互い違いに結合して主鎖を形成するｐ−フェニレンエチニレン類が知られている。この化合物は、剛直な直線状分子であり、π−π相互作用やファンデルワールス力等により複数の分子が自己組織化しやすい性質を持っている。このため、これらの化合物は溶解性が極めて低く、応用が難しいといった側面がある。そのような背景から、例えば特許文献２には、汎用溶媒への溶解性を付与することを目的として、主鎖を構成するフェニレン基に炭化水素残基を導入し、両端にチオール基、リン酸基、カルボキシル基、スルホン酸基、アミノ基、水酸基のいずれかを備えたフェニレンエチニレン化合物が提案されている。 As one of such π-conjugated oligomers, p-phenylene ethynylenes in which p-phenylene groups and ethynylene groups are alternately bonded to form a main chain are known. This compound is a rigid linear molecule, and has a property that a plurality of molecules are easily self-assembled by π-π interaction, van der Waals force, and the like. Therefore, these compounds have extremely low solubility and are difficult to apply. Against such a background, for example, in Patent Document 2, a hydrocarbon residue is introduced into a phenylene group constituting the main chain for the purpose of imparting solubility in a general-purpose solvent, and thiol groups and phosphoric acid are introduced at both ends. A phenylene ethynylene compound having any one of a group, a carboxyl group, a sulfonic acid group, an amino group and a hydroxyl group has been proposed.
ところで、自動車の排気ガスを初めとした様々な用途に応じて特定のガス成分を検出するガスセンサが各種提案されている。このようなガスセンサとしては、検出対象の化合物が金属やセラミック等からなるセンサの表面に結合することでその電気抵抗等といった物理特性が変化する性質を用いたもの（例えば特許文献３を参照）や、検出対象の化合物がセンサの表面に付着することでその色調が変化する性質を用いたもの（例えば特許文献４を参照）等が知られている。これらのセンサのうち色調の変化を生じるものは、検出対象の化合物の存在を目視で確認できるため、簡便なガスセンサとして有用である。 By the way, various gas sensors have been proposed that detect a specific gas component according to various uses such as automobile exhaust gas. Such a gas sensor uses a property that changes physical properties such as electric resistance when a compound to be detected is bonded to the surface of a sensor made of metal, ceramic, or the like (see, for example, Patent Document 3). , Those using the property of changing the color tone when the compound to be detected adheres to the surface of the sensor (see, for example, Patent Document 4) and the like are known. Among these sensors, those that cause a change in color tone are useful as a simple gas sensor because the presence of the compound to be detected can be visually confirmed.
本発明は、以上の状況に鑑みてなされたものであり、第一には、室温において液体として扱うことができ、従来よりも応用性の高められた新規なπ共役オリゴマーを提供することを目的とする。また本発明は、第二には、そのようなπ共役オリゴマーを用いることにより、酸性物質や塩基性物質の存在を光学的な変化で検出することのできるガスセンサ材料を提供することを目的とする。 The present invention has been made in view of the above circumstances. First, it is an object of the present invention to provide a novel π-conjugated oligomer that can be treated as a liquid at room temperature and has higher applicability than before. And. A second object of the present invention is to provide a gas sensor material capable of detecting the presence of an acidic substance or a basic substance by an optical change by using such a π-conjugated oligomer. ..
本発明者は、上記の課題を解決するために鋭意検討を重ねた結果、π共役オリゴマーであるｐ−フェニレンエチニレン（以下、「ｐ−」の記載を適宜省略する。）化合物において、分岐を有する炭素数８以上２０以下のアルキル基をベンゼン環に導入すると融点が室温まで低下し、物体の表面に塗布するのに適した化合物になること、及びこの化合物において、少なくとも一つのベンゼン環をピリジン環にする、又はベンゼン環に対して少なくとも一つの酸性基を導入することにより、それぞれ、酸性物質又は塩基性物質に曝露した際に色調や蛍光が変化するようになり、これらを検出するためのガスセンサ材料として有用であることを見出した。本発明は、このような知見に基づいて完成されたものであり、以下のようなものを提供する。 As a result of diligent studies to solve the above problems, the present inventor has branched the p-phenylene ethynylene (hereinafter, “p-” is appropriately omitted) compound which is a π-conjugated oligomer. Introducing an alkyl group having 8 to 20 carbon atoms into the benzene ring lowers the melting point to room temperature, making the compound suitable for application to the surface of an object, and in this compound, at least one benzene ring is pyridine. By forming a ring or introducing at least one acidic group into the benzene ring, the color tone and fluorescence change when exposed to an acidic substance or a basic substance, respectively, and for detecting these. It was found to be useful as a gas sensor material. The present invention has been completed based on such findings, and provides the following.
本発明は、下記一般式（１）で表す化合物である。
また本発明は、上記化合物を含むことを特徴とする発光材料でもある。 The present invention is also a light emitting material containing the above compound.
また本発明は、上記化合物を含むことを特徴とする電子材料でもある。 The present invention is also an electronic material characterized by containing the above compound.
また本発明は、下記一般式（３）で表す化合物を含むことを特徴とする酸感応型のガスセンサ材料でもある。
上記一般式（３）におけるＡｒがピリジン骨格であることが好ましい。 It is preferable that Ar in the general formula (3) has a pyridine skeleton.
本発明によれば、第一には、室温において液体として扱うことができ、従来よりも応用性の高められた新規なπ共役オリゴマーが提供される。また第二には、そのようなπ共役オリゴマーを用いることにより、酸性物質や塩基性物質の存在を光学的な変化で検出することのできるガスセンサ材料が提供される。 According to the present invention, firstly, a novel π-conjugated oligomer which can be treated as a liquid at room temperature and has higher applicability than the conventional one is provided. Secondly, by using such a π-conjugated oligomer, a gas sensor material capable of detecting the presence of an acidic substance or a basic substance by an optical change is provided.
以下、本発明に係る化合物、発光材料、電子材料、酸感応型のガスセンサ材料、及び塩基感応型のガスセンサ材料の各一実施形態についてそれぞれ説明する。なお、本発明は、以下の実施形態に限定されるものではなく、本発明の範囲において適宜変更を加えて実施することができる。 Hereinafter, each embodiment of the compound, the light emitting material, the electronic material, the acid-sensitive gas sensor material, and the base-sensitive gas sensor material according to the present invention will be described. The present invention is not limited to the following embodiments, and can be carried out with appropriate modifications within the scope of the present invention.
［化合物、発光材料、及び電子材料］
本発明の化合物は、下記一般式（１）で表されるオリゴフェニレンエチニレン誘導体である。オリゴフェニレンエチニレンのようなπ共役オリゴマーは、発達したπ共役系を備え、有機導電性材料、有機半導体、発光材料等への用途が期待される化合物である。しかしながら、発達したπ共役系を備えるということは、同時にπ−πスタッキングによる高度な自己組織性を備えることにもつながり、溶解性が極めて乏しい等、応用面で大きな不都合をもたらすものである。そのため、上記特許文献２記載の発明のように、オリゴフェニレンエチニレンに対して長鎖のアルキル基等を導入するなどの手段により溶解性を増加させることも検討されているが、そのような手段を用いたとしても、溶液として用いる以上、十分な濃度を確保するのが難しいことによる膜形成の困難さを伴うことがある。
[Compounds, luminescent materials, and electronic materials]
The compound of the present invention is an oligophenylene ethynylene derivative represented by the following general formula (1). Oligophenylene A π-conjugated oligomer such as ethynylene is a compound that has a developed π-conjugated system and is expected to be used in organic conductive materials, organic semiconductors, luminescent materials, and the like. However, having a developed π-conjugated system also leads to having a high degree of self-organization due to π-π stacking, which causes great inconvenience in terms of application such as extremely poor solubility. Therefore, as in the invention described in Patent Document 2, it has been studied to increase the solubility by means such as introducing a long-chain alkyl group or the like into oligophenylene ethynylene, but such means However, as long as it is used as a solution, it may be difficult to form a film because it is difficult to secure a sufficient concentration.
そのような背景のもと、本発明者らはオリゴフェニレンエチニレンへの化学修飾の検討を続けた結果、炭素数を多く含むアルキル基の中でも特に分岐を有するものをオリゴフェニレンエチニレンへ導入することにより、その融点を室温以下にまで下げることができることを見出した。このような融点降下を生じる理由として、長鎖分岐アルキルによるオリゴフェニレンエチニレン骨格の被覆が考えられる。すなわち、上記のようにオリゴフェニレンエチニレン骨格を有する化合物は高度な自己組織性を備え、これが融点の上昇や溶解性の不足をもたらすが、長鎖分岐アルキル基を備えることによりオリゴフェニレンエチニレン骨格が長鎖分岐アルキル基により被覆され、自己組織性が低下するものと考えられる。このようなオリゴフェニレンエチニレン誘導体であれば、それ自身が室温で液体であったり、室温で良好な溶液を形成することが可能であったりすることで、容易に膜形成をさせることが可能である。本発明に係るオリゴフェニレンエチニレン誘導体は、そのような知見に基づいて完成されたものであり、分岐を有する炭素数８以上２０以下のアルキル基を備えることを特徴とする。なお、本発明において室温とは概ね１５〜３０℃の範囲を想定するが、本発明に係る化合物の融点が３０℃以下、好ましくは１５℃以下、より好ましくは１０℃以下、さらに好ましくは０℃以下である、又はこれらの温度において安定な溶液を形成することができれば、本発明でいう「室温で液体である」ものとする。 Against such a background, as a result of continuing studies on chemical modification to oligophenylene ethynylene, the present inventors introduce an alkyl group containing a large number of carbon atoms having a particularly branched substance into oligophenylene ethynylene. By doing so, it was found that the melting point can be lowered to below room temperature. The reason why such a melting point drop occurs is considered to be the coating of the oligophenylene ethynylene skeleton with the long-chain branched alkyl. That is, as described above, the compound having an oligophenylene ethynylene skeleton has a high degree of self-organization, which causes an increase in melting point and insufficient solubility, but by having a long-chain branched alkyl group, the oligophenylene ethynylene skeleton is provided. Is coated with a long-chain branched alkyl group, and it is considered that the self-organization property is reduced. With such an oligophenylene ethynylene derivative, it is possible to easily form a film by itself being a liquid at room temperature or being able to form a good solution at room temperature. is there. The oligophenylene ethynylene derivative according to the present invention has been completed based on such findings, and is characterized by having a branched alkyl group having 8 to 20 carbon atoms. In the present invention, room temperature is assumed to be in the range of approximately 15 to 30 ° C., but the melting point of the compound according to the present invention is 30 ° C. or lower, preferably 15 ° C. or lower, more preferably 10 ° C. or lower, still more preferably 0 ° C. If the following, or if a stable solution can be formed at these temperatures, it is considered to be "liquid at room temperature" in the present invention.
上記一般式（１）中、各Ｒｐは、少なくとも一つのＲｐがＲ又はＯＲであることを条件に、それぞれ独立にＲ、ＯＲ、スルホ基、カルボキシル基、リン酸基、ヒドロキシル基、アンモニウム基、ピリジル基又はアミド基である。そして、各Ｒは、それぞれ独立に、分岐を有する炭素数８以上２０以下のアルキル基である。そのため、本発明の化合物は、分岐を有する炭素数８以上２０以下のアルキル基を一つ以上有することになる。ｍは０〜３の整数であり、ｎは０〜３の整数であり、ａ及びｂはともに１であり、ｃは１〜４の整数であり、ｄは１〜４の整数である。 In the above general formula (1), each Rp is independently R, OR, a sulfo group, a carboxyl group, a phosphate group, a hydroxyl group, an ammonium group, provided that at least one Rp is R or OR. It is a pyridyl group or an amide group. Each R is an alkyl group having a branch and having 8 or more carbon atoms and 20 or less carbon atoms independently. Therefore, the compound of the present invention has one or more branched alkyl groups having 8 or more carbon atoms and 20 or less carbon atoms. m is an integer of 0 to 3, n is an integer of 0 to 3, both a and b are 1 , c is an integer of 1 to 4 , and d is an integer of 1 to 4.
Ｒは、分岐を有する炭素数８以上２０以下のアルキル基である。「分岐を有する」とはアルキル基が枝分かれ構造を有することを意味し、この場合、直鎖として見たときに最も長いアルキル鎖となる主鎖に結合したアルキル基が分岐鎖（側鎖）となる。オリゴフェニレンエチニレン骨格を効果的に被覆するとの観点からは、上記分岐鎖がある程度の長さを有することが望ましく、分岐鎖が直鎖状でありかつその炭素数が４以上であることが好ましく挙げられ、分岐鎖がｎ−ヘキシル基であることがより好ましく挙げられる。より具体的には、中間体の入手容易性等の観点から、Ｒとして下記の２−ｎ−ヘキシルデシル基を特に好ましく挙げることができる。なお、下記の２−ｎ−ヘキシルデシル基を例として上記の主鎖と分岐鎖との関係を説明すれば、炭素数１０のデシル鎖（デシル基）が主鎖となり、炭素数６のヘキシル鎖（ヘキシル基）が分岐鎖（側鎖）となる。Ｒは、分岐を有する炭素数１０以上２０以下のアルキル基であることが好ましく、分岐を有する炭素数１２以上２０以下のアルキル基であることがより好ましい。 R is a branched alkyl group having 8 or more carbon atoms and 20 or less carbon atoms. "Having a branch" means that the alkyl group has a branched structure, and in this case, the alkyl group bonded to the main chain, which is the longest alkyl chain when viewed as a straight chain, is a branched chain (side chain). Become. From the viewpoint of effectively coating the oligophenylene ethynylene skeleton, it is desirable that the branched chain has a certain length, and the branched chain is preferably linear and has 4 or more carbon atoms. More preferably, the branched chain is an n-hexyl group. More specifically, the following 2-n-hexyldecyl group can be particularly preferably mentioned as R from the viewpoint of availability of the intermediate. To explain the relationship between the main chain and the branched chain using the following 2-n-hexyl decyl group as an example, the decyl chain (decyl group) having 10 carbon atoms becomes the main chain and the hexyl chain having 6 carbon atoms. (Hexyl group) becomes a branched chain (side chain). R is preferably an alkyl group having a branch and having 10 or more and 20 or less carbon atoms, and more preferably an alkyl group having a branch and having 12 or more and 20 or less carbon atoms.
上記一般式（１）で表す化合物のうち、上記一般式（１）において両末端のベンゼン環のそれぞれに１以上のＲ又はＯＲを持ち、ｍ個の繰り返しを有するベンゼン環のそれぞれに２以上のＲ又はＯＲを持ち、ｎ個の繰り返しを有するベンゼン環のそれぞれに２以上のＲ又はＯＲを持つものを好ましく例示できる。 Among the compounds represented by the general formula (1), in the above general formula (1), each of the benzene rings at both ends has 1 or more R or OR, and each of the benzene rings having m repetitions has 2 or more. Preferred examples thereof include those having R or OR and having 2 or more R or OR in each of the benzene rings having n repetitions.
上記一般式（１）中、Ａｒは、下記一般式（２）で表す２価の基である。 In the above general formula (1), Ar is a divalent group represented by the following general formula (2).
上記一般式（２）中、フェニレン環（すなわち２価のベンゼン環）に含まれる各炭素原子の１又は２が窒素原子で置換されてもよい。この場合、一般式（２）におけるベンゼン環はピリジン環やピリミジン環となる。これらピリジン環やピリミジン環を備えることにより、本発明の化合物は、後述する酸感応型のガスセンサ材料としても用いることが可能になる。 In the above general formula (2), 1 or 2 of each carbon atom contained in the phenylene ring (that is, the divalent benzene ring) may be replaced with a nitrogen atom. In this case, the benzene ring in the general formula (2) is a pyridine ring or a pyrimidine ring. By providing these pyridine ring and pyrimidine ring, the compound of the present invention can also be used as an acid-sensitive gas sensor material described later.
上記一般式（２）中、各Ｒａは、それぞれ独立に、Ｒ、ＯＲ、スルホ基、カルボキシル基、リン酸基、ヒドロキシル基、アンモニウム基、ピリジル基、アミド基、又は互いに隣り合った２つのＲａが結合して環構造を形成したものである。Ｒは、上記一般式（１）におけるものと同様である。互いに隣り合った２つのＲａが結合して形成される環構造は、一般式（２）におけるベンゼン環と縮合した環となり、ヘテロ原子を含んでもよい脂肪環又は芳香環である。このような環構造としては、ベンゼン環（一般式（２）におけるベンゼン環と縮合してナフタレン環となる。）や、２，１，３−チアジアゾール環（一般式（２）におけるベンゼン環と縮合して２，１，３−ベンゾチアジアゾール環となる。）が例示される。ｅは０〜４の整数であり、ｐは１〜３の整数である。 In the above general formula (2), each Ra is independently R, OR, a sulfo group, a carboxyl group, a phosphoric acid group, a hydroxyl group, an ammonium group, a pyridyl group, an amide group, or two Ras adjacent to each other. Are combined to form a ring structure. R is the same as that in the above general formula (1). The ring structure formed by combining two Ras adjacent to each other is a ring condensed with the benzene ring in the general formula (2), and is an alicyclic or aromatic ring which may contain a hetero atom. Such a ring structure includes a benzene ring (condensed with the benzene ring in the general formula (2) to form a naphthalene ring) and a 2,1,3-thiadiazole ring (condensed with the benzene ring in the general formula (2)). Then, it becomes 2,1,3-benzothiadiazole ring.) Is exemplified. e is an integer from 0 to 4, and p is an integer from 1 to 3.
上記一般式（１）で表す本発明の化合物は、エチニルベンゼンとジヨードベンゼンとの間で薗頭クロスカップリング反応を行って得ることができる。この場合、３核のオリゴフェニレンエチニレン化合物が得られる。また、ジエチニルベンゼンと、エチニルベンゼン及びジヨードベンゼンを薗頭クロスカップリング反応させたものとを薗頭クロスカップリングさせてもよい。この場合、５核のオリゴフェニレンエチニレン化合物が得られる。これらの反応例を下記スキーム１及びスキーム２に示す。また、下記スキーム１や２におけるジヨードベンゼンに代えてジヨードピリジン等の化合物を用いることにより、上記一般式（１）におけるＡｒのバリエーションとなる化合物を得ることができる。そのような例を下記スキーム３及びスキーム４に示す。なお、下記の各スキームにおけるＲとしては上記一般式（１）について説明したものを選択可能であるが、下記の各スキームでは説明のための便宜として、Ｒを上記２−ｎーヘキシルデシル基としている。また、下記の各スキームは説明のための一例であり、本発明が下記のスキームに記載された化合物に限定されることはない。 The compound of the present invention represented by the general formula (1) can be obtained by performing a Sonogashira cross-coupling reaction between ethynylbenzene and diiodobenzene. In this case, a trinuclear oligophenylene ethynylene compound is obtained. Further, the sonogashira cross-coupling reaction of diethynylbenzene and ethynylbenzene and diiodobenzene may be carried out. In this case, a pentanuclear oligophenylene ethynylene compound is obtained. Examples of these reactions are shown in Scheme 1 and Scheme 2 below. Further, by using a compound such as diiodopyridine instead of diiodobenzene in the following schemes 1 and 2, a compound that is a variation of Ar in the above general formula (1) can be obtained. Such an example is shown in Scheme 3 and Scheme 4 below. As R in each of the following schemes, the one described in the general formula (1) can be selected, but in each of the following schemes, R is used as the 2-n-hexyldecyl group for convenience of explanation. In addition, each of the following schemes is an example for explanation, and the present invention is not limited to the compounds described in the following schemes.
上記一般式（１）で表す化合物は、発達した共役系に基づく優れた発光特性、電気伝導性、半導体特性等を示す一方で、融点が低く、室温にて液体として存在させることが可能である。そのため、薄膜化等の加工が容易であり、有機ＥＬ、半導体、電子ペーパー、蛍光素子、二次電池等における電解液、液体導電体、水素吸蔵材料等への応用が期待される。特に、上記一般式（１）におけるＡｒとして環に窒素を含む化合物は、適当な酸化剤をドープすることにより電子が奪われ、導電性材料や半導体材料として用いることが可能である。これらのことから、本発明の化合物を含む発光材料や電子材料を作製することも可能である。このような発光材料や電子材料もまた本発明の一つである。なお、本発明において、「室温にて液体として存在させることが可能」とは、上記のように室温よりも融点が低いことのみならず、溶媒に対する溶解性が高く、室温にて良好な溶液を形成できることも含むものとする。 The compound represented by the above general formula (1) exhibits excellent luminescence properties, electrical conductivity, semiconductor properties, etc. based on the developed conjugated system, has a low melting point, and can be allowed to exist as a liquid at room temperature. .. Therefore, it is easy to process such as thinning, and it is expected to be applied to electrolytic solutions, liquid conductors, hydrogen storage materials, etc. in organic EL, semiconductors, electronic paper, fluorescent elements, secondary batteries and the like. In particular, the compound containing nitrogen in the ring as Ar in the general formula (1) is deprived of electrons by doping with an appropriate oxidizing agent, and can be used as a conductive material or a semiconductor material. From these facts, it is also possible to produce a luminescent material or an electronic material containing the compound of the present invention. Such a light emitting material or an electronic material is also one of the present inventions. In the present invention, "can exist as a liquid at room temperature" means not only that the melting point is lower than room temperature as described above, but also that the solution has high solubility in a solvent and is good at room temperature. It shall also include what can be formed.
［酸感応型のガスセンサ材料］
次に、本発明の酸感応型のガスセンサ材料について説明する。本発明の酸感応型のガスセンサ材料は、一般式（１）でＡｒとして表される（ポリ）フェニレン基において、フェニレン環に含まれる各炭素原子の少なくとも１つが窒素原子で置換された化合物を含むことを特徴とする。このような化合物は、一般式（１）でＡｒとして表される部分にピリジン骨格やピリミジン骨格等の塩基性基を含み、塩酸ガス等の酸性ガスが存在すると当該酸性ガスによりこれら塩基性基がプロトン化され、窒素原子が４級化される。これにより、分子内及び／又は分子間でのエネルギー移動を生じるようになり、蛍光発光の波長や、光吸収の波長がシフトする。本発明の酸感応型のガスセンサ材料は、このような原理に基づくものであり、上記一般式（１）で表す化合物の応用例ともいうことができる。以下、本発明の酸感応型のガスセンサ材料について説明するが、上記本発明の化合物の説明と重複する部分については、その説明を適宜省略する。
[Acid-sensitive gas sensor material]
Next, the acid-sensitive gas sensor material of the present invention will be described. The acid-sensitive gas sensor material of the present invention contains a compound in which at least one of each carbon atom contained in the phenylene ring is replaced with a nitrogen atom in the (poly) phenylene group represented by Ar in the general formula (1). It is characterized by that. Such a compound contains a basic group such as a pyridine skeleton or a pyrimidine skeleton in a portion represented by Ar in the general formula (1), and when an acid gas such as hydrochloric acid gas is present, the acidic gas causes these basic groups to be generated. It is protonated and the nitrogen atom is quaternized. As a result, energy transfer within and / or between molecules occurs, and the wavelength of fluorescence emission and the wavelength of light absorption shift. The acid-sensitive gas sensor material of the present invention is based on such a principle, and can be said to be an application example of the compound represented by the above general formula (1). Hereinafter, the acid-sensitive gas sensor material of the present invention will be described, but the description thereof will be omitted as appropriate for the portion overlapping with the description of the compound of the present invention.
本発明の酸感応型のガスセンサ材料は、下記一般式（３）で表す化合物を含むことを特徴とする。 The acid-sensitive gas sensor material of the present invention is characterized by containing a compound represented by the following general formula (3).
上記一般式（３）中、各Ｒｐは、それぞれ独立にＲ、ＯＲである。そして、各Ｒは、それぞれ独立に、分岐を有する炭素数８以上２０以下のアルキル基である。ｍは０〜３の整数であり、ｎは０〜３の整数であり、ａは１〜５の整数であり、ｂは１〜５の整数であり、ｃは１〜４の整数であり、ｄは１〜４の整数である。そのため、本発明の化合物は、分岐を有する炭素数８以上２０以下のアルキル基を有することになる。なお、上記一般式（１）では、Ｒｐの選択肢としてスルホ基、カルボキシル基といった酸性基が含まれていたが、本発明の酸感応型のガスセンサ材料ではこれらの酸性基の存在が酸性ガスの検出の障害になることも考えられるため、これらの酸性基はＲｐの選択肢として含まれない。 In the above general formula (3), each Rp is independently R and OR, respectively. Each R is an alkyl group having a branch and having 8 or more carbon atoms and 20 or less carbon atoms independently. m is an integer of 0 to 3, n is an integer of 0 to 3, a is an integer of 1 to 5, b is an integer of 1 to 5, and c is an integer of 1 to 4. d is an integer of 1 to 4. Therefore, the compound of the present invention has a branched alkyl group having 8 to 20 carbon atoms. In the above general formula (1), acidic groups such as a sulfo group and a carboxyl group were included as Rp options, but in the acid-sensitive gas sensor material of the present invention, the presence of these acidic groups detects acid gas. These acidic groups are not included as an option for Rp, as they may interfere with the above.
Ｒは、分岐を有する炭素数８以上２０以下のアルキル基である。これについては、上記一般式（１）と同様であるので説明を省略する。Ｒは、分岐を有する炭素数１０以上２０以下のアルキル基であることが好ましく、分岐を有する炭素数１２以上２０以下のアルキル基であることがより好ましい。また、上記一般式（３）で表す化合物のうち、上記一般式（３）において両末端のベンゼン環のそれぞれに１以上のＲ又はＯＲを持ち、ｍ個の繰り返しを有するベンゼン環のそれぞれに２以上のＲ又はＯＲを持ち、ｎ個の繰り返しを有するベンゼン環のそれぞれに２以上のＲ又はＯＲを持つものを好ましく例示できる点についても、上記一般式（１）と同様である。 R is a branched alkyl group having 8 or more carbon atoms and 20 or less carbon atoms. Since this is the same as the above general formula (1), the description thereof will be omitted. R is preferably an alkyl group having a branch and having 10 or more and 20 or less carbon atoms, and more preferably an alkyl group having a branch and having 12 or more and 20 or less carbon atoms. Further, among the compounds represented by the above general formula (3), in the above general formula (3), each of the benzene rings at both ends has 1 or more R or OR, and each of the m repeating benzene rings has 2 It is the same as the above general formula (1) in that a benzene ring having the above R or OR and having two or more R or OR in each of n repeating benzene rings can be preferably exemplified.
上記一般式（３）中、Ａｒは、下記一般式（４）で表す２価の基である。 In the above general formula (3), Ar is a divalent group represented by the following general formula (4).
上記一般式（４）中、フェニレン環に含まれる各炭素原子の少なくとも１つが窒素原子で置換されている。このため、上記一般式（４）で表される上記Ａｒで表される部分には、ピリジン骨格やピリミジン骨格等の塩基性基が含まれる。そしてこれらの塩基性基は、塩酸ガス等の酸性ガスに曝された際に窒素原子がプロトン化され４級化される。これにより、分子内及び／又は分子間でのエネルギー移動を生じるようになり、蛍光発光の波長や、光吸収の波長がシフトするようになる。本発明の酸感応型のガスセンサ材料は、本化合物のこのような性質を利用したものであり、当該化合物自身の色調や蛍光発光の色調の変化といった、目視可能な変化により酸性物質の存在を検出することが可能になる。勿論、本化合物は発達した共役系を備えるので、こうした変化を電気的に検出することも可能である。 In the above general formula (4), at least one of each carbon atom contained in the phenylene ring is substituted with a nitrogen atom. Therefore, the portion represented by Ar represented by the general formula (4) contains a basic group such as a pyridine skeleton or a pyrimidine skeleton. When these basic groups are exposed to an acid gas such as hydrochloric acid gas, the nitrogen atom is protonated and quaternized. As a result, energy transfer within and / or between molecules occurs, and the wavelength of fluorescence emission and the wavelength of light absorption shift. The acid-sensitive gas sensor material of the present invention utilizes such properties of the present compound, and detects the presence of an acidic substance by visible changes such as changes in the color tone of the compound itself and the color tone of fluorescence emission. It becomes possible to do. Of course, since this compound has a developed conjugated system, it is possible to detect such changes electrically.
各Ｒａは、それぞれ独立に、Ｒ、ＯＲ、又は互いに隣り合った２つのＲａが結合して環構造を形成したものである。Ｒは、上記一般式（３）におけるものと同様である。互いに隣り合った２つのＲａが結合して形成される環構造は、一般式（４）におけるベンゼン環と縮合した環となり、ヘテロ原子を含んでもよい脂肪環又は芳香環である。このような環構造としては、ベンゼン環（一般式（４）におけるベンゼン環と縮合してナフタレン環となる。）や、２，１，３−チアジアゾール環（一般式（４）におけるベンゼン環と縮合して２，１，３−ベンゾチアジアゾール環となる。）が例示される。ｅは０〜３の整数であり、ｐは１〜３の整数である。 Each Ra is independently formed by R, OR, or two Ras adjacent to each other to form a ring structure. R is the same as that in the above general formula (3). The ring structure formed by combining two Ras adjacent to each other is a ring condensed with the benzene ring in the general formula (4), and is an alicyclic or aromatic ring which may contain a hetero atom. Such a ring structure includes a benzene ring (condensed with the benzene ring in the general formula (4) to form a naphthalene ring) and a 2,1,3-thiadiazole ring (condensed with the benzene ring in the general formula (4)). Then, it becomes 2,1,3-benzothiadiazole ring.) Is exemplified. e is an integer of 0 to 3, and p is an integer of 1 to 3.
上記一般式（３）におけるＡｒとして、より具体的には、ピリジン骨格であることを好ましく挙げることができる。なお、ｐが１よりも大きな整数である場合、Ａｒに含まれるいずれかの環がピリジン骨格であれば、「Ａｒがピリジン骨格である」ものとする。 More specifically, the Ar in the general formula (3) can be preferably a pyridine skeleton. When p is an integer larger than 1, and any ring contained in Ar has a pyridine skeleton, it is assumed that "Ar is a pyridine skeleton".
また、上記一般式（３）及び（４）におけるアルキル基の分岐鎖の炭素数が４以上であることが好ましいことや、分岐鎖がｎ−ヘキシル基であることがより好ましく挙げられる点については、上記一般式（１）及び（２）と同様である。 Further, it is preferable that the branched chain of the alkyl group in the above general formulas (3) and (4) has 4 or more carbon atoms, and more preferably that the branched chain is an n-hexyl group. , The same as the above general formulas (1) and (2).
上記一般式（３）で表す化合物は、室温にて液体であり得る程度に融点が低いので、表面への塗布等といった加工性に優れる。また、酸性ガスの存在を、蛍光や色調の変化という目視観測可能な変化により高感度に示すことができる。よって、このような化合物を含んでなる本発明の酸感応型のガスセンサ材料は、実用性に優れた材料として有用である。なお、上記「室温にて液体であり得る」との表現が、室温よりも融点が低いことのみならず、溶媒に対する溶解性が高く、室温にて良好な溶液を形成できることも含むことは既に述べた通りである。 Since the compound represented by the general formula (3) has a low melting point to the extent that it can be liquid at room temperature, it is excellent in processability such as coating on a surface. In addition, the presence of acid gas can be shown with high sensitivity by visually observable changes such as changes in fluorescence and color tone. Therefore, the acid-sensitive gas sensor material of the present invention containing such a compound is useful as a material having excellent practicality. It has already been mentioned that the above expression "may be liquid at room temperature" includes not only that the melting point is lower than room temperature but also that it has high solubility in a solvent and can form a good solution at room temperature. That's right.
［塩基感応型のガスセンサ材料］
次に、本発明の塩基感応型のガスセンサ材料について説明する。本発明の塩基感応型のガスセンサ材料は、一般式（１）で表すオリゴフェニレンエチニレン化合物のうち、酸性置換基を備えた化合物を含むことを特徴とする。このような化合物は、アンモニア等の塩基性ガスに曝されると当該酸性置換基が脱プロトンされアニオンになる。これにより、分子内及び／又は分子間でのエネルギー移動を生じるようになり、蛍光発光の波長や光吸収の波長がシフトする。本発明の塩基感応型のガスセンサ材料は、このような原理に基づくものであり、上記一般式（１）で表す化合物の応用例ともいうことができる。以下、本発明の塩基感応型のガスセンサ材料について説明するが、上記本発明の化合物の説明と重複する部分については、その説明を適宜省略する。
[Base-sensitive gas sensor material]
Next, the base-sensitive gas sensor material of the present invention will be described. The base-sensitive gas sensor material of the present invention is characterized by containing a compound having an acidic substituent among the oligophenylene ethynylene compounds represented by the general formula (1). When such a compound is exposed to a basic gas such as ammonia, the acidic substituent is deprotonated to become an anion. As a result, energy transfer within and / or between molecules occurs, and the wavelength of fluorescence emission and the wavelength of light absorption shift. The base-sensitive gas sensor material of the present invention is based on such a principle, and can be said to be an application example of the compound represented by the above general formula (1). Hereinafter, the base-sensitive gas sensor material of the present invention will be described, but the description thereof will be omitted as appropriate for the portion overlapping with the description of the compound of the present invention.
本発明の塩基感応型ガスセンサ材料は、下記一般式（５）で表す化合物を含むことを特徴とする。 The base-sensitive gas sensor material of the present invention is characterized by containing a compound represented by the following general formula (5).
上記一般式（５）中、各Ｒｐは、少なくとも一つのＲｐがＲ又はＯＲであることを条件に、それぞれ独立にＲ、ＯＲ、スルホ基、カルボキシル基、リン酸基、ヒドロキシル基、アンモニウム基、ピリジル基又はアミド基である。そして、各Ｒは、それぞれ独立に、分岐を有する炭素数８以上２０以下のアルキル基である。そのため、本発明の化合物は、分岐を有する炭素数８以上２０以下のアルキル基を一つ以上有することになる。ｍは０〜３の整数であり、ｎは０〜３の整数であり、ａは１〜５の整数であり、ｂは１〜５の整数であり、ｃは１〜５の整数であり、ｄは１〜５の整数である。 In the above general formula (5), each Rp is independently R, OR, a sulfo group, a carboxyl group, a phosphate group, a hydroxyl group, an ammonium group, provided that at least one Rp is R or OR. It is a pyridyl group or an amide group. Each R is an alkyl group having a branch and having 8 or more carbon atoms and 20 or less carbon atoms independently. Therefore, the compound of the present invention has one or more branched alkyl groups having 8 or more carbon atoms and 20 or less carbon atoms. m is an integer of 0 to 3, n is an integer of 0 to 3, a is an integer of 1 to 5, b is an integer of 1 to 5, and c is an integer of 1 to 5. d is an integer of 1-5.
Ｒは、分岐を有する炭素数８以上２０以下のアルキル基である。これについては、上記一般式（１）と同様であるので説明を省略する。Ｒは、分岐を有する炭素数１０以上２０以下のアルキル基であることが好ましく、分岐を有する炭素数１２以上２０以下のアルキル基であることがより好ましい。また、上記一般式（５）で表す化合物のうち、上記一般式（５）において両末端のベンゼン環のそれぞれに１以上のＲ又はＯＲを持ち、ｍ個の繰り返しを有するベンゼン環のそれぞれに２以上のＲ又はＯＲを持ち、ｎ個の繰り返しを有するベンゼン環のそれぞれに２以上のＲ又はＯＲを持つものを好ましく例示できる点についても、上記一般式（１）と同様である。 R is a branched alkyl group having 8 or more carbon atoms and 20 or less carbon atoms. Since this is the same as the above general formula (1), the description thereof will be omitted. R is preferably an alkyl group having a branch and having 10 or more and 20 or less carbon atoms, and more preferably an alkyl group having a branch and having 12 or more and 20 or less carbon atoms. Further, among the compounds represented by the general formula (5), in the above general formula (5), each of the benzene rings at both ends has 1 or more R or OR, and each of the m repeating benzene rings has 2 or more. It is the same as the above general formula (1) in that a benzene ring having the above R or OR and having two or more R or OR in each of n repeating benzene rings can be preferably exemplified.
上記一般式（５）中、Ａｒは、下記一般式（６）で表す２価の基である。 In the above general formula (5), Ar is a divalent group represented by the following general formula (6).
上記一般式（６）中、各Ｒａは、それぞれ独立に、Ｒ、ＯＲ、スルホ基、カルボキシル基、リン酸基、ヒドロキシル基、アンモニウム基、ピリジル基、アミド基、又は互いに隣り合った２つのＲａが結合して環構造を形成したものである。Ｒは、上記一般式（５）におけるものと同様である。互いに隣り合った２つのＲａが結合して形成される環構造は、一般式（６）におけるベンゼン環と縮合した環となり、ヘテロ原子を含んでもよい脂肪環又は芳香環である。このような環構造としては、ベンゼン環（一般式（６）におけるベンゼン環と縮合してナフタレン環となる。）や、２，１，３−チアジアゾール環（一般式（６）におけるベンゼン環と縮合して２，１，３−ベンゾチアジアゾール環となる。）が例示される。ｅは０〜４の整数であり、ｐは１〜３の整数である。 In the above general formula (6), each Ra is independently R, OR, a sulfo group, a carboxyl group, a phosphoric acid group, a hydroxyl group, an ammonium group, a pyridyl group, an amide group, or two Ras adjacent to each other. Are combined to form a ring structure. R is the same as that in the above general formula (5). The ring structure formed by bonding two Ras adjacent to each other is a ring condensed with the benzene ring in the general formula (6), and is an alicyclic or aromatic ring which may contain a hetero atom. Such a ring structure includes a benzene ring (condensed with the benzene ring in the general formula (6) to form a naphthalene ring) and a 2,1,3-thiadiazole ring (condensed with the benzene ring in the general formula (6)). Then, it becomes 2,1,3-benzothiadiazole ring.) Is exemplified. e is an integer from 0 to 4, and p is an integer from 1 to 3.
ここで、一般式（５）及び（６）において、各Ｒｐ及び各Ｒａのうちの少なくとも一つは、スルホ基、カルボキシル基、リン酸基又はヒドロキシル基である。本発明の塩基感応型ガスセンサに含まれる化合物がこれらの酸性置換基を備えることにより、アンモニア等の塩基性ガスに曝された際にこれら酸性置換基が脱プロトンされてアニオンになり、それに伴って分子内及び／又は分子間でのエネルギー移動が生じ、蛍光発光の波長や光吸収の波長がシフトするようになる。 Here, in the general formulas (5) and (6), at least one of each Rp and each Ra is a sulfo group, a carboxyl group, a phosphate group or a hydroxyl group. When the compound contained in the base-sensitive gas sensor of the present invention is provided with these acidic substituents, these acidic substituents are deprotonated to become anions when exposed to a basic gas such as ammonia, and accordingly. Energy transfer occurs within and / or between molecules, and the wavelength of fluorescence emission and the wavelength of light absorption shift.
上記一般式（５）及び（６）におけるアルキル基の分岐鎖の炭素数が４以上であることが好ましいことや、分岐鎖がｎ−ヘキシル基であることがより好ましく挙げられる点については、上記一般式（１）及び（２）と同様である。 The above-mentioned points that it is preferable that the branched chain of the alkyl group in the general formulas (5) and (6) has 4 or more carbon atoms and that the branched chain is an n-hexyl group are more preferable. It is the same as the general formulas (1) and (2).
上記一般式（５）で表す化合物は、室温にて液体であり得る程度に融点が低いので、表面への塗布等といった加工性に優れる。また、塩基性ガスの存在を、蛍光や色調の変化という目視観測可能な変化により高感度に示すことができる。よって、このような化合物を含んでなる本発明の塩基感応型のガスセンサ材料は、実用性に優れた材料として有用である。なお、上記「室温にて液体であり得る」との表現が、室温よりも融点が低いことのみならず、溶媒に対する溶解性が高く、室温にて良好な溶液を形成できることも含むことは既に述べた通りである。 Since the compound represented by the general formula (5) has a low melting point to the extent that it can be liquid at room temperature, it is excellent in processability such as coating on a surface. In addition, the presence of basic gas can be shown with high sensitivity by visually observable changes such as changes in fluorescence and color tone. Therefore, the base-sensitive gas sensor material of the present invention containing such a compound is useful as a material having excellent practicality. It has already been mentioned that the above expression "may be liquid at room temperature" includes not only that the melting point is lower than room temperature but also that it has high solubility in a solvent and can form a good solution at room temperature. That's right.
以下に実施例を挙げて本発明をさらに具体的に説明するが、本発明はこれらの実施例に何ら限定されるものではない。なお、以下の合成例では、１Ｈ−ＮＭＲ、１３Ｃ−ＮＭＲ、ＦＴ−ＩＲ、ＵＶ−ｖｉｓ、ＦＬ測定等により構造を確認した。また、反応に用いた各種の溶媒は、定法により乾燥させ、蒸留したものである。 Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples. In the following synthesis example, the structure was confirmed by 1 H-NMR, 13 C-NMR, FT-IR, UV-vis, FL measurement and the like. The various solvents used in the reaction were dried by a conventional method and distilled.
［ＯＰＥ−Ｐｙ１の合成］
上記スキーム３に記載したＯＰＥ−Ｐｙ１を下記合成例１〜４の各ステップを経ることにより合成した。
[Synthesis of OPE-Py1]
OPE-Py1 described in the above scheme 3 was synthesized by going through each of the steps of Synthesis Examples 1 to 4 below.
［合成例１］
４−ヨードフェノール０．５０ｇ（２．２５ｍｍｏｌ）、１−クロロ−２−ｎ−ヘキシルデカン０．９４ｇ（１１．３ｍｍｏｌ）及びジメチルホルムアミド（ＤＭＦ）１０ｍＬを反応容器に加え１００℃で撹拌し、その中へ炭酸カリウム１．５６ｇ（１１．３ｍｍｏｌ）及びヨウ化カリウム２５ｍｇを加え、１５０℃で３日間撹拌しながら還流させた。その後、吸引濾過で固形分を除いた後、溶液にジクロロメタンを加えて分液ロートでジクロロメタン層を分取し、これを硫化マグネシウムで乾燥させた後、溶媒を留去した。その後、カラムクロマトグラフィー（留出液：ヘキサン）で精製し、化合物３を０．７５ｇ（収率７５．０％）得た。 Add 0.50 g (2.25 mmol) of 4-iodophenol, 0.94 g (11.3 mmol) of 1-chloro-2-n-hexyldecane and 10 mL of dimethylformamide (DMF) to the reaction vessel and stir at 100 ° C. 1.56 g (11.3 mmol) of potassium carbonate and 25 mg of potassium iodide were added to the mixture, and the mixture was refluxed at 150 ° C. for 3 days with stirring. Then, after removing the solid content by suction filtration, dichloromethane was added to the solution, the dichloromethane layer was separated by a separating funnel, dried over magnesium sulfide, and then the solvent was distilled off. Then, it was purified by column chromatography (distillate: hexane) to obtain 0.75 g (yield 75.0%) of compound 3.
［合成例２］
化合物３（０．２５ｇ、０．５６３ｍｍｏｌ）及びトリエチルアミン（ＴＥＡ、５ｍＬ）を反応容器に加えて溶解させ、これにヨウ化銅（Ｉ）３．２ｍｇを加えて窒素気流下で３０分間撹拌した。その後、ビス（トリフェニルホスフィン）パラジウム（ＩＩ）ジクロリド１１．８ｍｇ及びトリメチルシリルアセチレン０．１５ｍＬ（０．６７５ｍｍｏｌ）を加えて、６０℃で１日間撹拌還流させ、得られた反応溶液を減圧濃縮して溶媒を除去した。カラムクロマトグラフィー（留出液：ヘキサン）で精製し、化合物４を０．２０ｇ（収率８７．０％）得た。 Compound 3 (0.25 g, 0.563 mmol) and triethylamine (TEA, 5 mL) were added to the reaction vessel to dissolve them, and 3.2 mg of copper (I) iodide was added thereto, and the mixture was stirred under a nitrogen stream for 30 minutes. Then, 11.8 mg of bis (triphenylphosphine) palladium (II) dichloride and 0.15 mL (0.675 mmol) of trimethylsilylacetylene were added, and the mixture was stirred and refluxed at 60 ° C. for 1 day, and the obtained reaction solution was concentrated under reduced pressure. The solvent was removed. Purification by column chromatography (distillate: hexane) gave 0.20 g (yield 87.0%) of compound 4.
［合成例３］
化合物４（０．２０ｇ、０．４８２ｍｍｏｌ）及びテトラヒドロフラン（ＴＨＦ）５ｍＬを反応容器に入れて溶解させ、これにテトラブチルアンモニウムフロリド（ＴＢＡＦ）０．５８ｍＬ（０．５７９ｍｍｏｌ）を加えて遮光下で３０分間撹拌し、得られた反応溶液を減圧濃縮して溶媒を除去した。カラムクロマトグラフィー（留出液：ヘキサン）で精製し、化合物５を０．１５ｇ（収率９３．８％）得た。 Compound 4 (0.20 g, 0.482 mmol) and 5 mL of tetrahydrofuran (THF) are placed in a reaction vessel to dissolve them, and 0.58 mL (0.579 mmol) of tetrabutylammonium fluoride (TBAF) is added thereto under shading. The mixture was stirred for 30 minutes, and the obtained reaction solution was concentrated under reduced pressure to remove the solvent. Purification by column chromatography (distillate: hexane) gave 0.15 g (yield 93.8%) of compound 5.
［合成例４］
２，５−ジヨードピリジン０．０６ｇ（０．１７０ｍｍｏｌ）、化合物５（０．１４ｇ、０．４０９ｍｍｏｌ）及びトルエン１０ｍＬを反応容器に入れて溶解させ、これにヨウ化銅（Ｉ）０．９ｍｇを加えて窒素気流下で３０分間撹拌した。テトラキス（トリフェニルホスフィン）パラジウム５．９ｍｇ及びＴＥＡ５ｍＬを加えて９０℃で１日間撹拌しながら還流させ、得られた反応溶液を減圧濃縮して溶媒を除去した。カラムクロマトグラフィー（留出液：ジクロロメタン：ヘキサン＝１：１）で精製し、ＯＰＥ−Ｐｙ１を０．０８ｇ（収率６１．５％）得た。得られたＯＰＥ−Ｐｙ１は、室温で液体だった。 0.06 g (0.170 mmol) of 2,5-diiodopyridine, compound 5 (0.14 g, 0.409 mmol) and 10 mL of toluene were placed in a reaction vessel to dissolve them, and 0.9 mg of copper (I) iodide was dissolved therein. Was added and stirred for 30 minutes under a nitrogen stream. 5.9 mg of tetrakis (triphenylphosphine) palladium and 5 mL of TEA were added and refluxed at 90 ° C. for 1 day with stirring, and the obtained reaction solution was concentrated under reduced pressure to remove the solvent. Purification by column chromatography (distillate: dichloromethane: hexane = 1: 1) gave 0.08 g (yield 61.5%) of OPE-Py1. The obtained OPE-Py1 was liquid at room temperature.
［ＯＰＥ−Ｐｙ２の合成］
上記スキーム３に記載したＯＰＥ−Ｐｙ２を下記合成例５〜９の各ステップを経ることにより合成した。
[Synthesis of OPE-Py2]
The OPE-Py2 described in Scheme 3 above was synthesized by going through each of the steps of Synthesis Examples 5 to 9 below.
［合成例５］
３，６−ジヨード−１，４−ヒドロキノン０．５５ｇ（１．５３ｍｍｏｌ）、１−クロロ−２−ｎ−ヘキシルデカン１．００ｇ（３．８３ｍｍｏｌ）及びＤＭＦ１０ｍＬを反応容器に加え、溶解するまで１００℃で撹拌した。これに炭酸カリウム２．１２ｇ（１５．３ｍｍｏｌ）を加え、１５０℃で３日間撹拌しながら還流させた。溶液にジクロロメタンを加えて分液ロートでジクロロメタン層を分取し、これを硫化マグネシウムで乾燥させた後、溶媒を留去した。その後、カラムクロマトグラフィー（留出液：ヘキサン）で精製し、化合物６を０．１９ｇ（収率１５．３％）得た。 Add 0.55 g (1.53 mmol) of 3,6-diiodot-1,4-hydroquinone, 1.00 g (3.83 mmol) of 1-chloro-2-n-hexyldecane and 10 mL of DMF to the reaction vessel and add to the reaction vessel at 100 ° C. until dissolution. Was stirred with. To this, 2.12 g (15.3 mmol) of potassium carbonate was added, and the mixture was refluxed at 150 ° C. for 3 days with stirring. Dichloromethane was added to the solution, and the dichloromethane layer was separated by a separating funnel, which was dried over magnesium sulfide, and then the solvent was distilled off. Then, it was purified by column chromatography (distillate: hexane) to obtain 0.19 g (yield 15.3%) of compound 6.
［合成例６］
化合物６（０．３５ｇ、０．４３２ｍｍｏｌ）、化合物５（０．０７ｇ、０．２１６ｍｍｏｌ）及びトルエン１０ｍＬを反応容器に加えて溶解させ、これにヨウ化銅（Ｉ）１．２ｍｇを加えて窒素気流下で３０分間撹拌した。テトラキス（トリフェニルホスフィン）パラジウム７．５ｍｇ及びＴＥＡ５ｍＬを加えて９０℃で１日間撹拌しながら還流させ、得られた反応溶液を減圧濃縮して溶媒を除去した。カラムクロマトグラフィー（留出液：ジクロロメタン：ヘキサン＝１：３）で精製し、化合物７を０．１３ｇ（収率５９．１％）得た。 Compound 6 (0.35 g, 0.432 mmol), compound 5 (0.07 g, 0.216 mmol) and 10 mL of toluene were added to the reaction vessel to dissolve them, and 1.2 mg of copper (I) iodide was added thereto to dissolve nitrogen. The mixture was stirred under air for 30 minutes. 7.5 mg of tetrakis (triphenylphosphine) palladium and 5 mL of TEA were added and refluxed at 90 ° C. for 1 day with stirring, and the obtained reaction solution was concentrated under reduced pressure to remove the solvent. Purification by column chromatography (distillate: dichloromethane: hexane = 1: 3) gave 0.13 g (yield 59.1%) of compound 7.
［合成例７］
２，５−ジヨードピリジン０．２０ｇ（０．６０４ｍｍｏｌ）及びＴＥＡ１０ｍＬを反応溶液に入れて溶解させ、これにヨウ化銅（Ｉ）３．５ｍｇを加えて窒素気流下で３０分間撹拌した。ビス（トリフェニルホスフィン）パラジウムジクロリド１２．７ｍｇ及びトリメチルシリルアセチレン０．２０ｍＬ（１．４５ｍｍｏｌ）を加えて６０℃で１日間撹拌還流し、得られた反応溶液を減圧濃縮して溶媒を除去した。カラムクロマトグラフィー（留出液：ヘキサン：ジクロロメタン＝１：１）で精製し、化合物８を０．１９ｇ（収率１１９％）得た。 0.20 g (0.604 mmol) of 2,5-diiodopyridine and 10 mL of TEA were added to the reaction solution to dissolve them, 3.5 mg of copper (I) iodide was added thereto, and the mixture was stirred under a nitrogen stream for 30 minutes. 12.7 mg of bis (triphenylphosphine) palladium dichloride and 0.20 mL (1.45 mmol) of trimethylsilylacetylene were added, and the mixture was stirred under reflux at 60 ° C. for 1 day, and the obtained reaction solution was concentrated under reduced pressure to remove the solvent. Purification by column chromatography (distillate: hexane: dichloromethane = 1: 1) gave 0.19 g (yield 119%) of compound 8.
［合成例８］
化合物８（０．１９ｇ、０．７００ｍｍｏｌ）及びＴＨＦ１０ｍＬを反応容器に入れて溶解させた後、ＴＢＡＦ１．６８ｍＬ（１．６８ｍｍｏｌ）を加えて遮光下で３０分間撹拌し、得られた反応溶液を減圧濃縮して溶媒を除去した。カラムクロマトグラフィー（留出液：ジクロロメタン）で精製し、化合物９を０．０６ｇ（収率６６．７％）得た。 Compound 8 (0.19 g, 0.700 mmol) and 10 mL of THF were placed in a reaction vessel to dissolve them, then 1.68 mL (1.68 mmol) of TBAF was added and stirred for 30 minutes under shading, and the obtained reaction solution was depressurized. The mixture was concentrated to remove the solvent. Purification by column chromatography (distillate: dichloromethane) gave 0.06 g (yield 66.7%) of compound 9.
［合成例９］
化合物９（４．０ｍｇ、０．０３１１ｍｍｏｌ）、化合物７（０．０７ｇ、０．０６８３ｍｍｏｌ）及びトルエン５ｍＬを反応容器に入れて溶解させ、これにヨウ化銅（Ｉ）０．２ｍｇを加えて窒素気流下で３０分間撹拌した。テトラキス（トリフェニルホスフィン）パラジウム１．１ｍｇ及びＴＥＡ５ｍＬを加えて９０℃で１日間撹拌しながら還流させ、得られた反応溶液を減圧濃縮して溶媒を除去した。カラムクロマトグラフィー（留出液：ジクロロメタン：ヘキサン＝１：１）で精製し、ＯＰＥ−Ｐｙ２を０．０３ｇ（収率５０．０％）得た。得られたＯＰＥ−Ｐｙ２は、室温で液体だった。 Compound 9 (4.0 mg, 0.0311 mmol), compound 7 (0.07 g, 0.0683 mmol) and toluene 5 mL were placed in a reaction vessel to dissolve them, and 0.2 mg of copper (I) iodide was added thereto to dissolve nitrogen. The mixture was stirred under air for 30 minutes. 1.1 mg of tetrakis (triphenylphosphine) palladium and 5 mL of TEA were added and refluxed at 90 ° C. for 1 day with stirring, and the obtained reaction solution was concentrated under reduced pressure to remove the solvent. Purification by column chromatography (distillate: dichloromethane: hexane = 1: 1) gave 0.03 g (yield 50.0%) of OPE-Py2. The obtained OPE-Py2 was liquid at room temperature.
［ＯＰＥ１の合成］
上記スキーム１に記載したＯＰＥ１を下記合成例１０により合成した。
[Synthesis of OPE1]
OPE1 described in Scheme 1 above was synthesized according to Synthesis Example 10 below.
［合成例１０］
化合物６（０．０７ｇ、０．０９７３ｍｍｏｌ）、化合物５（０．０８ｇ、０．２３４ｍｍｏｌ）及びトルエン１０ｍＬを反応容器に加えて溶解させ、これにヨウ化銅（Ｉ）０．６ｍｇを加えて３０分間撹拌した。テトラキス（トリフェニルホスフィン）パラジウム３．４ｍｇ及びＴＥＡ５ｍＬを加えて９０℃で１日間撹拌しながら還流させ、得られた反応溶液を減圧濃縮して溶媒を除去した。カラムクロマトグラフィー（留出液：ジクロロメタン：ヘキサン＝１：４）で精製し、ＯＰＥ１を０．０４ｇ（収率３３．３％）得た。得られたＯＰＥ１は、室温で液体だった。 Compound 6 (0.07 g, 0.0973 mmol), compound 5 (0.08 g, 0.234 mmol) and 10 mL of toluene were added to the reaction vessel to dissolve them, and 0.6 mg of copper (I) iodide was added thereto to dissolve 30. Stir for minutes. 3.4 mg of tetrakis (triphenylphosphine) palladium and 5 mL of TEA were added and refluxed at 90 ° C. for 1 day with stirring, and the obtained reaction solution was concentrated under reduced pressure to remove the solvent. Purification by column chromatography (distillate: dichloromethane: hexane = 1: 4) gave 0.04 g (yield 33.3%) of OPE1. The obtained OPE1 was liquid at room temperature.
［ＯＰＥ２の合成］
上記スキーム２に記載したＯＰＥ２を下記合成例１１により合成した。
[Synthesis of OPE2]
OPE2 described in Scheme 2 above was synthesized according to Synthesis Example 11 below.
［合成例１１］
１，４−ジエチニルベンゼン１０（５．６ｍｇ、０．０４４４ｍｍｏｌ）、化合物７（０．１０ｇ、０．０９７６ｍｍｏｌ）及びトルエン１０ｍＬを反応容器に入れて溶解させ、これにヨウ化銅（Ｉ）０．３ｍｇを加えて窒素気流下で３０分間撹拌した。テトラキス（トリフェニルホスフィン）パラジウム１．５ｍｇ及びＴＥＡ５ｍＬを加えて９０℃で１日間撹拌しながら還流させ、得られた反応溶液を減圧濃縮して溶媒を除去した。カラムクロマトグラフィー（留出液：ジクロロメタン：ヘキサン＝１：４）で精製し、ＯＰＥ２を０．０３ｇ（収率３３．３％）得た。得られたＯＰＥ２は、室温で液体だった。 1,4-Diethynylbenzene 10 (5.6 mg, 0.0444 mmol), compound 7 (0.10 g, 0.0976 mmol) and 10 mL of toluene were placed in a reaction vessel to dissolve them, and copper (I) iodide (I) 0 was dissolved therein. .3 mg was added and the mixture was stirred under a nitrogen stream for 30 minutes. 1.5 mg of tetrakis (triphenylphosphine) palladium and 5 mL of TEA were added and refluxed at 90 ° C. for 1 day with stirring, and the obtained reaction solution was concentrated under reduced pressure to remove the solvent. Purification by column chromatography (distillate: dichloromethane: hexane = 1: 4) gave 0.03 g (yield 33.3%) of OPE2. The obtained OPE2 was liquid at room temperature.
［ＯＰＥ−Ｂｔ１の合成］
上記スキーム４に記載したＯＰＥ−Ｂｔ１を下記合成例１２により合成した。
[Synthesis of OPE-Bt1]
OPE-Bt1 described in Scheme 4 above was synthesized according to Synthesis Example 12 below.
［合成例１２］
化合物１１（０．０９ｇ、０．１８２ｍｍｏｌ）、化合物５（０．１５ｇ、０．４３８ｍｍｏｌ）及びトルエン１０ｍＬを反応容器に加えて溶解させ、これにヨウ化銅（Ｉ）１．０ｍｇを加えて窒素気流下で３０分間撹拌した。テトラキス（トリフェニルホスフィン）パラジウム６．３ｍｇ及びＴＥＡ５ｍＬを加えて９０℃で１日間撹拌しながら還流させ、得られた反応溶液を減圧濃縮して溶媒を除去した。カラムクロマトグラフィー（留出液：ジクロロメタン：ヘキサン＝１：２）で精製し、ＯＰＥ−Ｂｔ１を０．０５ｇ（収率２７．８％）得た。得られたＯＰＥ−Ｂｔ１は、室温で液体だった。 Compound 11 (0.09 g, 0.182 mmol), compound 5 (0.15 g, 0.438 mmol) and toluene 10 mL were added to the reaction vessel to dissolve them, and 1.0 mg of copper (I) iodide was added thereto to dissolve nitrogen. The mixture was stirred under air for 30 minutes. 6.3 mg of tetrakis (triphenylphosphine) palladium and 5 mL of TEA were added and refluxed at 90 ° C. for 1 day with stirring, and the obtained reaction solution was concentrated under reduced pressure to remove the solvent. Purification by column chromatography (distillate: dichloromethane: hexane = 1: 2) gave 0.05 g (yield 27.8%) of OPE-Bt1. The obtained OPE-Bt1 was liquid at room temperature.
［ＯＰＥ−Ｂｔ２の合成］
上記スキーム４に記載したＯＰＥ−Ｂｔ２を下記合成例１３〜１５により合成した。
[Synthesis of OPE-Bt2]
OPE-Bt2 described in Scheme 4 above was synthesized according to the following Synthesis Examples 13 to 15.
［合成例１３］
化合物１１（０．１６ｇ、０．２９６ｍｍｏｌ）及びＴＥＡ１０ｍＬを反応容器に加えて６０℃に加熱して溶解させ、これにヨウ化銅（Ｉ）１．７ｍｇを加えて窒素気流下で３０分間撹拌した。その後、ビス（トリフェニルホスフィン）パラジウム（ＩＩ）ジクロリド６．２ｍｇ及びトリメチルシリルアセチレン０．１５ｍＬ（０．６７５ｍｍｏｌ）を加えて、６０℃で１日間撹拌還流させ、得られた反応溶液を減圧濃縮して溶媒を除去した。カラムクロマトグラフィー（留出液：ジクロロメタン：ヘキサン＝１：２）で精製し、化合物１２を０．１０ｇ（収率７１．４％）得た。 Compound 11 (0.16 g, 0.296 mmol) and TEA 10 mL were added to the reaction vessel and heated to 60 ° C. to dissolve them, 1.7 mg of copper (I) iodide was added thereto, and the mixture was stirred under a nitrogen stream for 30 minutes. .. Then, 6.2 mg of bis (triphenylphosphine) palladium (II) dichloride and 0.15 mL (0.675 mmol) of trimethylsilylacetylene were added, and the mixture was stirred and refluxed at 60 ° C. for 1 day, and the obtained reaction solution was concentrated under reduced pressure. The solvent was removed. Purification by column chromatography (distillate: dichloromethane: hexane = 1: 2) gave 0.10 g (yield 71.4%) of compound 12.
［合成例１４］
化合物１２（０．１０ｇ、０．２０８ｍｍｏｌ）及びＴＨＦ５ｍＬを反応容器に入れて溶解させ、これにＴＢＡＦ０．５０ｍＬ（０．４９９ｍｍｏｌ）を加えて遮光下で３０分間撹拌し、得られた反応溶液を減圧濃縮して溶媒を除去した。カラムクロマトグラフィー（留出液：ジクロロメタン：ヘキサン＝１：１）で精製し、化合物１３を０．０２ｇ（収率２８．６％）得た。 Compound 12 (0.10 g, 0.208 mmol) and THF (5 mL) were placed in a reaction vessel to dissolve them, TBAF 0.50 mL (0.499 mmol) was added thereto, and the mixture was stirred for 30 minutes under shading, and the obtained reaction solution was depressurized. The mixture was concentrated to remove the solvent. Purification by column chromatography (distillate: dichloromethane: hexane = 1: 1) gave 0.02 g (yield 28.6%) of compound 13.
［合成例１５］
化合物１３（０．０２ｇ、０．０５７７ｍｍｏｌ）、化合物７（０．１３ｇ、０．１２７ｍｍｏｌ）及びトルエン７ｍＬを反応容器に入れて溶解させ、これにヨウ化銅（Ｉ）０．３ｍｇを加えて窒素気流下で３０分間撹拌した。テトラキス（トリフェニルホスフィン）パラジウム２．０ｍｇ及びＴＥＡ５ｍＬを加えて９０℃で１日間撹拌しながら還流させ、得られた反応溶液を減圧濃縮して溶媒を除去した。カラムクロマトグラフィー（留出液：ジクロロメタン：ヘキサン＝１：２）で精製し、ＯＰＥ−Ｂｔ２を０．０２ｇ（収率１６．７％）得た。得られたＯＰＥ−Ｂｔ２は、室温で液体だった。 Compound 13 (0.02 g, 0.0577 mmol), compound 7 (0.13 g, 0.127 mmol) and toluene 7 mL were placed in a reaction vessel to dissolve them, and 0.3 mg of copper (I) iodide was added thereto to dissolve nitrogen. The mixture was stirred under air for 30 minutes. 2.0 mg of tetrakis (triphenylphosphine) palladium and 5 mL of TEA were added and refluxed at 90 ° C. for 1 day with stirring, and the obtained reaction solution was concentrated under reduced pressure to remove the solvent. Purification by column chromatography (distillate: dichloromethane: hexane = 1: 2) gave 0.02 g (yield 16.7%) of OPE-Bt2. The obtained OPE-Bt2 was liquid at room temperature.
［蛍光特性］
上記の手順で合成されたＯＰＥ１、ＯＰＥ２、ＯＰＥ−Ｐｙ１、ＯＰＥ−Ｐｙ２、ＯＰＥ−Ｂｔ１及びＯＰＥ−Ｂｔ２のそれぞれについて、クロロホルム溶液としたときの紫外可視吸収スペクトル及び蛍光スペクトル、並びに化合物自体を石英板に塗布して薄膜としたときの紫外可視吸収」スペクトル及び蛍光スペクトルを測定した。その測定により得られた極大吸収波長、極大発光波長、及び薄膜時の蛍光の色調を表１に記載した。
[Fluorescence characteristics]
For each of OPE1, OPE2, OPE-Py1, OPE-Py2, OPE-Bt1 and OPE-Bt2 synthesized by the above procedure, the ultraviolet-visible absorption spectrum and fluorescence spectrum when prepared as a chloroform solution, and the compound itself are quartz plates. The "ultraviolet-visible absorption" spectrum and the fluorescence spectrum when applied to a thin film were measured. Table 1 shows the maximum absorption wavelength, the maximum emission wavelength, and the color tone of fluorescence at the time of thin film obtained by the measurement.
［Ｔｇ測定］
上記の手順で合成されたＯＰＥ１、ＯＰＥ２、ＯＰＥ−Ｐｙ１、ＯＰＥ−Ｐｙ２、ＯＰＥ−Ｂｔ１及びＯＰＥ−Ｂｔ２のそれぞれについて、示差走査熱量計（ＤＳＣ）を用いてガラス転移温度（Ｔｇ）を求めた。ＤＳＣ測定は窒素雰囲気下で行い、走査範囲を−５０℃〜１５０℃とし、１０℃／分で昇温させて行った。測定結果を表１のＴｇ欄に示す。
[Tg measurement]
The glass transition temperature (Tg) was determined for each of OPE1, OPE2, OPE-Py1, OPE-Py2, OPE-Bt1 and OPE-Bt2 synthesized by the above procedure using a differential scanning calorimeter (DSC). The DSC measurement was carried out in a nitrogen atmosphere, the scanning range was set to −50 ° C. to 150 ° C., and the temperature was raised at 10 ° C./min. The measurement results are shown in the Tg column of Table 1.
表１に示すように、いずれの化合物もＴｇは０℃以下であり、室温で液体状態であることがわかる。また、それぞれの化合物の蛍光色調は、π共役系の長さや、一般式（１）におけるＡｒの構造に応じて様々に変化させることができ、本発明の化合物によれば三原色の蛍光発光を揃えることも可能なことがわかる。 As shown in Table 1, it can be seen that each compound has a Tg of 0 ° C. or lower and is in a liquid state at room temperature. Further, the fluorescence color tone of each compound can be variously changed according to the length of the π-conjugated system and the structure of Ar in the general formula (1), and according to the compound of the present invention, the fluorescence emission of the three primary colors is aligned. It turns out that it is also possible.
クロロホルム溶液と薄膜とでは分子の存在する環境が大きく異なるが、特に異なる要素として分子の密度を挙げることができる。すなわち、溶液中では分子が希薄な状態で存在するが薄膜では分子が密に存在するため、自己組織性のある分子であれば薄膜において自己組織化しやすい状況にあるといえる。このような場合、溶液中では自己組織化が生じにくい一方で薄膜では自己組織化を生じ、そのような場合には分子間エネルギー移動による蛍光波長の変化が観察される。本発明の化合物はいずれもＴｇが０℃以下であり、この点で自己組織化を生じにくいといえるが、ＯＰＥ１、ＯＰＥ２、ＯＰＥ−Ｐｙ１、ＯＰＥ−Ｐｙ２、及びＯＰＥ−Ｂｔ２では、いずれも薄膜時の蛍光が溶液中よりも長波長側にシフトしており、薄膜のような厳しい環境では自己組織性を示すことがわかる。その一方でＯＰＥ−Ｂｔ１では、薄膜の蛍光波長が溶液におけるそれと同じであり、薄膜のような厳しい環境でも自己組織化を生じにくいことがわかる。 The environment in which molecules exist differs greatly between the chloroform solution and the thin film, but the density of the molecules can be mentioned as a particularly different factor. That is, it can be said that the molecules exist in a dilute state in the solution, but the molecules are densely present in the thin film, so that the self-assembling molecules are likely to be self-assembled in the thin film. In such a case, self-assembly is unlikely to occur in the solution, while self-assembly occurs in the thin film, and in such a case, a change in the fluorescence wavelength due to intermolecular energy transfer is observed. All of the compounds of the present invention have a Tg of 0 ° C. or lower, and it can be said that self-assembly is unlikely to occur in this respect. However, in OPE1, OPE2, OPE-Py1, OPE-Py2, and OPE-Bt2, when the film is thin. It can be seen that the fluorescence of is shifted to the longer wavelength side than in the solution, and exhibits self-organization in a harsh environment such as a thin film. On the other hand, in OPE-Bt1, the fluorescence wavelength of the thin film is the same as that in the solution, and it can be seen that self-assembly is unlikely to occur even in a harsh environment such as a thin film.
［酸性ガス曝露時の吸収及び蛍光変化］
ＯＰＥ−Ｐｙ１及びＯＰＥ−Ｐｙ２のそれぞれについて、化合物を石英板に塗布して薄膜とした状態で塩酸（ＨＣｌ）ガスに曝露させ、吸収波長及び蛍光波長の変化を観察した。その結果を表２に示す。なお、表２における吸収波長及び蛍光波長は、いずれも吸収極大及び蛍光極大における波長である。
[Absorption and fluorescence changes when exposed to acid gas]
For each of OPE-Py1 and OPE-Py2, the compound was coated on a quartz plate to form a thin film, which was exposed to hydrochloric acid (HCl) gas, and changes in absorption wavelength and fluorescence wavelength were observed. The results are shown in Table 2. The absorption wavelength and the fluorescence wavelength in Table 2 are the wavelengths at the absorption maximum and the fluorescence maximum.
表２に示すように、ＨＣｌガスの曝露により吸収波長及び蛍光波長の両方が長波長側にシフトし、その変化は目視でも観察できた。このことから、ＯＰＥ−Ｐｙ１やＯＰＥ−Ｐｙ２を含んでなる本発明に係る酸感応型ガスセンサの有用性が理解できる。 As shown in Table 2, both the absorption wavelength and the fluorescence wavelength were shifted to the long wavelength side due to the exposure to the HCl gas, and the change could be visually observed. From this, it is possible to understand the usefulness of the acid-sensitive gas sensor according to the present invention, which comprises OPE-Py1 and OPE-Py2.
次に、ＨＣｌガスに曝露されたＯＰＥ−Ｐｙ１及びＯＰＥ−Ｐｙ２の薄膜に対して、それぞれ塩基性であるピリジンガスを曝露させた。そのときの吸収スペクトル及び蛍光スペクトルの変化を図１に示す。図１は、ＨＣｌに曝露されたＯＰＥ−Ｐｙ１及びＯＰＥ−Ｐｙ２の薄膜に対してピリジンガスを曝露させたときの蛍光スペクトルの変化を示し、図１（ａ）はＯＰＥ−Ｐｙ１のスペクトル変化を示し、図１（ｂ）はＯＰＥ−Ｐｙ２のスペクトル変化を示す。図１（ａ）及び（ｂ）ともに、点線はもとの薄膜時の蛍光スペクトルであり、「ＨＣｌ」はＨＣｌガス曝露後の蛍光スペクトルであり、「Ｐｙ」はＨＣｌガス曝露後のサンプルにピリジンガスを曝露させたときの蛍光スペクトルである。 Next, the thin films of OPE-Py1 and OPE-Py2 exposed to HCl gas were exposed to pyridine gas, which is basic, respectively. The changes in the absorption spectrum and the fluorescence spectrum at that time are shown in FIG. FIG. 1 shows the change in the fluorescence spectrum when pyridine gas was exposed to the thin films of OPE-Py1 and OPE-Py2 exposed to HCl, and FIG. 1 (a) shows the change in the spectrum of OPE-Py1. , FIG. 1 (b) shows the spectral change of OPE-Py2. In both FIGS. 1A and 1B, the dotted line is the fluorescence spectrum of the original thin film, “HCl” is the fluorescence spectrum after exposure to HCl gas, and “Py” is the pyridine in the sample after exposure to HCl gas. It is a fluorescence spectrum when the gas is exposed.
図１（ａ）及び（ｂ）に示すように、ＨＣｌガスに曝露されることにより長波長側へシフトしていた蛍光スペクトルが、ピリジンガスに曝露されることにより短波長側へシフトし、もとの蛍光スペクトルに近いスペクトルになることがわかる。特に、図１（ｂ）に示すＯＰＥ−Ｐｙ２では、ほぼ完全にもとの蛍光スペクトルへ戻ることがわかる。また、ＯＰＥ−Ｐｙ２に関しては、ＨＣｌガスとピリジンガスとの曝露を何度も繰り返した際に同じ変化を繰り返したことから、サイクル耐久性を有することもわかった。 As shown in FIGS. 1 (a) and 1 (b), the fluorescence spectrum shifted to the long wavelength side by exposure to the HCl gas is shifted to the short wavelength side by exposure to the pyridine gas. It can be seen that the spectrum is close to the fluorescence spectrum of. In particular, in OPE-Py2 shown in FIG. 1 (b), it can be seen that the original fluorescence spectrum is almost completely restored. It was also found that OPE-Py2 has cycle durability because the same change was repeated when the exposure to HCl gas and pyridine gas was repeated many times.
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