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Hoʻohui ʻia nā apo ʻala 5-silikona i ka hope

Manaʻo manaʻo

18 min read Via cen.acs.org

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Ua Hoʻokō ʻia kahi Moʻo Kemika Kahiko o nā Keneturi

No hoʻokahi haneli mau makahiki, ua manaʻo ʻia ʻo ka ʻala - ka ʻano mechanical quantum e hāʻawi i ka paʻa kūʻokoʻa i kekahi mau molekala ʻano apo. Ua ʻike ʻia ʻo Benzene i ka makahiki 1825 a ua hoʻoponopono ʻia e ʻAukake Kekulé i ka makahiki 1865, ua lilo ia i keiki hoʻolaha no nā pūhui ʻala, a ua kūkulu nā hanauna o ka poʻe chemist i nā ʻoihana holoʻokoʻa ma kāna ʻano kalapona. Akā, ma kahi hoʻokō ʻāina e kākau hou ana i nā lula o ka kemika inorganic, ua synthesized ka poʻe noiʻi i ke apo piha ʻelima mau lālā i haku ʻia me nā ʻātoma silika. ʻO kēia anion pentasilacyclopentadienide ʻaʻole ia he lanakila synthetic wale nō, akā he ʻano hoʻololi i ke ʻano o ka hoʻomaopopo ʻana i ka hoʻopaʻa ʻana o ke kemika, ke kūpaʻa molekala, a me ka hiki ʻole o ke kilikakika i hoʻohana ʻole ʻia ma mua o kāna hana i nā semiconductor.

Aromaticity: ʻO ka mea huna paʻa i kūkulu ʻia i ke kemika hou

I mea e mahalo ai i ke kumu nui o ka apo silicon aromatic apo, pono mua oe e hoomaopopo i ka mea a ka aromaticity e haawi mai ai. ʻAʻole ʻano apo wale nā ​​molekala ʻala - loaʻa iā lākou kahi hoʻonohonoho electron kūikawā kahi e hoʻokaʻawale ʻia ai nā electrons pi ma ka hale apo holoʻokoʻa, e hana ana i "kapua" o ka puʻupuʻu electron kaʻana like e hoʻohaʻahaʻa loa i ka ikehu o ka mole. Hoʻopili kēia hoʻokaʻawale ʻana i ka lula a Hückel, ʻo ia ka mea e hōʻike ana i kahi molekala paʻa, cyclic me (4n + 2) pi electrons - kahi n he helu ʻino ʻole - e hōʻike i ka hoʻokūpaʻa ʻala. No ka cyclopentadienide anion (ka mana kalapona), ʻo ia hoʻi, 6 pi electrons i hoʻokaʻawale ʻia ma nā ʻātoma kalapona 5.

ʻAʻole mea liʻiliʻi kēia ikehu hoʻopaʻa. ʻO Benzene, ke apo kalapona ʻeono, ʻoi aku ka paʻa o 150 kJ/mol ma mua o ka cyclohexatriene hypothetical me nā mea paʻa pālua i hoʻopaʻa ʻia. ʻO ia ʻano paʻa ʻē aʻe ke kumu e ʻoi ai ka nui o nā pūhui ʻala i ka kemika lāʻau (ʻoi aku ma mua o 85% o nā lāʻau i ʻāpono ʻia aia ma kahi o hoʻokahi apo ʻala ʻala), ʻo ia ka iwi kuamoʻo o nā polymers synthetic, a lilo i mau mea waena nui i nā kaʻina hana kemika ʻoihana waiwai he mau haneli piliona kālā i kēlā me kēia makahiki.

O ka cyclopentadienide anion — ke apo ʻala ʻelima o ke kalapona — ua like ke kahua. Hoʻokumu ia i ke kumu o ke kemika metallocene, e hiki ai i nā catalysts e like me ferrocene i hoʻololi i ke kemika organometallic ma hope o ko lākou ʻike ʻia ʻana i ka makahiki 1951. ʻO ka nīnau i hoʻopiʻi i ka poʻe kemika no nā makahiki he pololei: inā hiki i ke kalapona ke hana i kēia, no ke aha e hiki ʻole ai ke silikona?

Ka Pale Silika: No ke aha e pale aku ai nā mea kaumaha i ka ʻala

Noho pono ka Silicon ma lalo o ke kalapona ma ka papaʻaina, kaʻana like ʻehā valence electrons, a hana i nā geometries hoʻopaʻa tetrahedral i ka hapa nui o nā pūhui. Ma ka pepa, pono ia e hana i nā apo ʻala. I ka hoʻomaʻamaʻa ʻana, ʻoi aku ka nui o ka radius atomika nui o ke silikona (1.17 Å me ka 0.77 Å o ke kalapona) a me nā orbital 3p hou aʻe e hana i nā mea keakea nui i ke ʻano o ka pi-orbital ʻaoʻao maikaʻi loa e koi ai i ka ʻala.

Silicon-silicon paʻa paʻa manaʻo ia lakou iho hiki ole a hiki i ka hui o Robert West ma ke Kulanui o Wisconsin synthesized ka mua stable disilene ma 1981. I ia manawa, keia mau paʻa paʻa lua ua mamao loa nawaliwali a oi aku ka hoʻoikaika ma mua o ko lākou mau hoa kalapona. He 310 kJ/mol ka Si=Si i hoʻohālikelike ʻia me 614 kJ/mol no C=C. No ka loaʻa ʻana o ka hoʻopaʻa pi i hoʻokaʻawale ʻia ma waena o ke apo holoʻokoʻa o nā ʻātoma silikona, pono e lanakila i kēia nāwaliwali ʻoiai e mālama ana i ka geometry planar pono no ka overlap orbital.

ʻO nā hoʻāʻo mua ma mua o 40+ mau makahiki i hana i nā apo ʻala ʻala i hoʻololi ʻia i ke silika, nā heterocycles i loko o ka silika, a me nā ʻano like ʻole. Akā, ʻo ke apo ʻala homoatomic piha loa - ʻo kēlā me kēia ʻātoma i loko o ke apo he silika - ua mau ke kohola keʻokeʻo o ka hui nui. ʻElua ʻāpana o ka luʻi: hoʻohui ʻana i ke apo lima-silikona me ka helu electron pololei a paʻa pono ke ʻano.

Ka Paʻa ʻana: Paʻa Paʻa ʻEnekinia Ma o ka Palekana Steric

Ua hilina'i ka synthesis holomua ma kahi ho'olālā i lilo i mea ma'amau gula no ka ho'opa'a 'ana i nā pūhui hui nui reactive: nā pū'ulu pani nui. Ma ka hoʻopili ʻana i nā ligands hāʻawi electron nui i kēlā me kēia ʻātoma silika i ke apo, ua hoʻokō ka hui noiʻi i ʻekolu mau pahuhopu koʻikoʻi i ka manawa like. Ua pale kino nā pūʻulu nui i nā mea hoʻopaʻa silika-silikona reactive mai nā reagents o waho, ua kōkua ko lākou mau waiwai hāʻawi electron i ka hoʻopaʻa ʻana i ka hoʻopiʻi maikaʻi ʻole o ka anion, a ua hoʻokō ka nui steric i ka geometry kokoke-planar i koi ʻia no ka delocalization pi.

Na ke ano o ka pentasilacyclopentadienide synthesized i hōʻoia i ke ʻano ʻala ma o nā ʻano hana kūʻokoʻa he nui:

  • X-ray crystallographyhōʻike ʻia nā lōʻihi pili Si-Si kokoke like a puni ke apo (~ 2.25 Å), e kūlike me ka hoʻopaʻa delocalized ma mua o ka hoʻololi ʻana i nā paʻa hoʻokahi a me nā paʻa pālua
  • Nuclear magnetic resonance (NMR) spectroscopyhōʻike i nā hiʻohiʻona deshielding hiʻohiʻona e like me ke apo ʻala ʻala
  • Nucleus-independent chemical shift (NICS) calculationsi hoʻopuka i nā waiwai maikaʻi ʻole ma ke kikowaena apo, kahi hōʻailona helu helu i ʻae ʻia no ka ʻono
  • UV-visible spectroscopy hōʻike ʻia nā hiʻohiʻona absorption e kūlike me ka hoʻololi ʻana o ka pi-electron i hoʻokaʻawale ʻia ma waena o ke kaʻa silikona
  • Ka helu ʻana i ke kumumanaʻo Density functional theory (DFT)ua hoʻopaʻa ʻia i ka ikehu hoʻokūpaʻa ʻala, manaʻo ʻia ma 50-70 kJ/mol

ʻOiai ʻoi aku ka haʻahaʻa o ka ikehu stabilization ʻaʻala ma mua o ka 150 kJ/mol o benzene, ua lawa ia e hoʻokaʻawale a ʻike ʻia ka pūhui ma ka lumi wela ma lalo o ke ʻano o ka lewa inert - he hana kupaianaha no kahi mole i manaʻo ʻia ʻaʻole hiki ke noho ma ke ʻano paʻa.

Ma waho aʻe o ka Papa Hana Hana: Nā Manaʻo ʻOiaʻiʻo

Ke wehe nei ka hoʻohuihui ʻana o nā apo silikona ʻala i nā ala noiʻi e ʻoi aku ana ma mua o ka ʻimi ʻike kula. Hiki i nā pūhui ʻala hoʻokumu i ka silikoni ke hōʻike i nā waiwai uila i ʻokoʻa loa mai ko lākou mau mea hoʻohālikelike kalapona, me nā mea hiki ke hoʻohana ʻia i nā ʻoihana waiwai nui.

ʻO ka loaʻa ʻana o nā mea ʻala-silikona āpau ʻaʻole ia e hoʻohui i kahi pūhui hou i ka catalog - hoʻokumu ia i kahi papa hou loa o ka hoʻolālā molekala. ʻO kēlā me kēia palapala noi i kūkulu ʻia ma luna o ka ʻono kalapona i nā makahiki he 160 i hala iho nei, loaʻa iā ia kahi mea hoʻohālikelike ma muli o ke silika e kali nei e ʻimi ʻia, ʻo kēlā me kēia me nā waiwai uila, optical, a me catalytic.

I loko o ka ʻenehana semiconductor, kahi i noho aliʻi ai ke silika ma ke ʻano he kumu kumu, hiki i nā pūhui silikona ʻala ke lawelawe ma ke ʻano he ʻāpana uila molecular-scale. Hiki i nā electrons pi i hoʻokaʻawale ʻia i loko o kēia mau apo ke hana i ka hoʻopiʻi ma nā ala ʻokoʻa mai ka silika nui, e hāʻawi ana i nā ala e hele ai i nā mea uila molekala a me nā substrates computing quantum. Me ka mākeke semiconductor honua i manaʻo ʻia e ʻoi aku ma mua o $1 trillion i ka makahiki 2030, ʻoiai ʻo ka piʻi ʻana o ka hoʻonui ʻia ʻana o nā mea uila molekala i hoʻokumu ʻia i ke kilika e loaʻa i nā hopena ʻoihana nui.

Ma nā photovoltaics, hiki ke hana nā apo ʻala silika ma ke ʻano he chromophores ʻohi māmā. ʻO kā lākou waiwai hoʻoheheʻe a me ka hoʻokuʻu ʻana - hiki ke hoʻololi ʻia ma o ka hoʻololi ʻana - hiki ke hiki i nā papa hou o nā diodes māmā māmā (OLEDs) i hoʻokumu ʻia i ke kilikakika a i ʻole nā ​​mea hoʻonaʻauao o ka lā e hoʻopaʻa i ka ʻokoʻa ma waena o nā photovoltaics silika kahiko a me nā ʻenehana solar e puka mai ana.

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Ka Nīnau Hoʻopuka: Silicon Metallocenes on the Horizon

Malia paha ʻo ka manaʻo hoihoi loa i ka hiki ke loaʻa nā metallocenes ma muli o ke silika. Hoʻokumu ka anion cyclopentadienide o Carbon i nā pūhui sanwika me ka aneane kēlā me kēia metala hoʻololi, a ʻo kēia mau metallocenes he mau mea hoʻoheheʻe nui i ka kemika polymer. ʻO Ziegler-Natta a me ka metallocene catalysts e kākoʻo i ka hana ʻana o 100 miliona tone polyethylene a me polypropylene i kēlā me kēia makahiki - he mākeke ma kahi o $200 biliona.

Inā hiki i ka pentasilacyclopentadienide ke hoʻohui i nā metala hoʻololi e like me ke ʻano o kāna analog kalapona, e loaʻa i nā metallocenes silika ka hopena i nā waiwai steric a me nā waiwai uila. Na ke apo silika nui e hana i ka "bite angle" ākea a puni ke kikowaena metala, hiki ke hiki i nā koho hou i loko o ka polymerization olefin, CH activation, a me nā hoʻololi catalytic ʻē aʻe. ʻOiai ʻo ka hoʻomaikaʻi haʻahaʻa ʻana o ka hana catalyst ma kēia ʻano ʻoihana, ua unuhi ʻia i nā piliona kālā ma ka waiwai a me ka emi nui o ka hoʻohana ʻana i ka ikehu a me ka ʻōpala.

Hōʻike nā haʻawina helu helu mua e hiki nō i nā metallocenes silika ke hōʻike i nā waiwai magnetic i hoʻonui ʻia i ko lākou mau hoa kalapona, e wehe ana i nā noi ma ka spintronics a me nā mea mālama ʻikepili magnetic. He ʻōpiopio ke kahua, akā ke waiho ʻia nei ke kumu kumu noʻonoʻo ma waena o nā hui noiʻi lehulehu.

Hoʻokele i ka Paʻakikī o nā Hana Noiʻi Hou

Hōʻike ʻia nā mea hoʻokūkū e like me nā apo silikona ʻono i ka paʻakikī o ka noiʻi ʻepekema hou - nā papahana multiyear e pili ana i nā hui cross-disciplinary, nā mea kani pipiʻi, ka hoʻokō ʻana i ke kānāwai, ka hoʻokele hāʻawi, a me ka hui pū ʻana o ka honua. ʻO nā hui noiʻi a me nā mea hoʻomaka e kūʻai i kā lākou ʻike e kū nei i nā luʻina hana e kūʻē i kēlā me kēia ʻoihana waena: ka ʻimi ʻana i nā hanana o nā hana ikaika, ka mālama ʻana i ke kūʻai ʻana a me nā pilina o nā mea kūʻai aku no nā kemika kūikawā a me nā lako, ka lawelawe ʻana i nā HR no nā hui huli o nā postdocs a me nā haumāna puka kula, a me ka mālama ʻana i nā moʻolelo no ka pale ʻana i ka waiwai naʻauao.

Nā papahana e like me Mewayz e hoʻopuka pololei i kēia paʻakikī hana. Me 207 mau modules i hoʻohui ʻia e pili ana i ka CRM, invoicing, hoʻokele papahana, HR, a me ka analytics, hāʻawi ʻo Mewayz i nā hui noiʻi i hoʻokahi ʻōnaehana e hoʻokele i ka ʻaoʻao ʻoihana o ka hana hou. Ma mua o ka hoʻopili ʻana i nā pāpalapala, nā kaulahao leka uila, a me nā mea lako polokalamu i hoʻokaʻawale ʻia, hiki i nā hui ke hahai i nā milestones o ka papahana, mālama i nā invoice hoʻolako no nā reagents laboratory, hoʻonohonoho i nā papa manawa hui, a hoʻopuka i nā hōʻike kālā e koi ʻia e nā keʻena kālā - mai kahi kahua hoʻokahi. No nā hui 138,000+ e hoʻohana nei iā Mewayz ma ke ao holoʻokoʻa, ʻo kēia ʻano o ka mana hoʻokele kikowaena ʻo ia ka liʻiliʻi o ka manawa ma luna o ka hoʻokele a ʻoi aku ka nui o ka manawa e koi ai i nā palena o ka mea hiki ke loaʻa i ka ʻepekema.

He aha ka mea e hiki mai ana: He mau mea huna hou aʻe i ka Papa Manawa

ʻO ka hana kūleʻa ʻana o kahi apo ʻala silikona āpau e hāpai koke i ka nīnau: pehea nā mea ʻē aʻe o ka Pūʻulu 14? ʻO Germanium, tin, a me ke alakaʻi i kaʻana like i ka hoʻonohonoho ʻehā-valence-electron o ke silika, a hāʻawi kēlā me kēia i kāna mau pilikia ponoʻī no ka hoʻokō ʻana i nā ʻōnaehana apo ʻala paʻa. ʻO nā apo ʻala Germanium, ʻo ia hoʻi, ua manaʻo ʻia i kēia manawa he pahuhopu kokoke loa, ʻoiai ke kūlana waena o germanium ma waena o ke silikoni a me nā mea kaumaha.

Ma waho aʻe o ka Pūʻulu 14, ua hoʻonui ʻia ka manaʻo o ka mea ʻala i nā pūʻulu boron (nā boranes a me nā carboranes e hōʻike ana i ka ʻala ʻekolu-dimensional), nā apo phosphorus, a me nā ʻōnaehana ʻala-metala āpau e like me ka Al4²⁻ tetraanion i ʻike mua ʻia i ka makahiki 2001. nā poloka kūkulu hale me nā waiwai ʻaʻole hiki ke hana hou ʻia e nā ʻōnaehana kumu kalapona wale nō.

Ke hoʻopaʻa ʻia nei ka hoʻohuihui ʻana o ka pentasilacyclopentadienide i kahi ʻano ākea o ka kemika hou: ka ʻimi ʻōnaehana o nā mea hui nui no nā kumu hoʻopaʻa i mālama mua ʻia no ke kalapona. I loko o nā makahiki ʻelua i hala iho nei, ua hoʻokō ʻia nā pūhui paʻa i loaʻa nā paʻa triple silicon-silicon, phosphorus-phosphorus triple bond, a me nā paʻa ʻekolu boron-boron. ʻO kēlā me kēia mea i ʻike ʻia ma mua o nā ʻumi makahiki o ka hoʻāʻo ʻole ʻana a me ka manaʻo kānalua, a ua wehe kēlā me kēia i nā ala hou no ka hoʻolālā ʻana i nā mea.

ʻO ka mea e koʻikoʻi ai ke apo silikona ʻala ʻo kona pili pono ʻana i kekahi o nā manaʻo koʻikoʻi ʻoihana kemika. ʻAʻole ʻo ka Aromaticity kahi abstraction hoʻonaʻauao - ʻo ia ka waiwai molekala e kākoʻo ana i nā lāʻau lapaʻau, plastics, dyes, explosives, agrochemicals, a me nā mea uila. ʻO ka hoʻonui ʻana i kēia waiwai i ke silika ʻaʻole e hoʻopau wale i kahi lālani ma ka papa puke puke. Hoʻomaka ʻo ia i kahi au hou o ke kemika silika kahi e hoʻonui loa ʻia ai ka mana o ka element ma mua o nā wafers crystalline i loko o kā mākou mau ʻāpana kamepiula a i loko o ke aupuni o ka hoʻolālā molekala a hiki i kēia manawa, pili wale i ke kalapona.

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Nīnau pinepine

He aha ke apo silikona ʻala?

ʻO ke apo silikonʻa ʻala he molela kahi i hoʻokumu ʻia ai nā ʻātoma silika i hale paʻa, ʻano apo me kahi paʻa "ʻala" kūikawā, kahi waiwai i manaʻo ʻia no ka carbon wale nō. Hoʻopili ʻia kēia i nā electrons e kaʻana like a puni ke apo, e hoʻoikaika ʻole ai ia. Hoʻonui maoli kēia ʻike i ka manaʻo o ka mea ʻala ma mua o ke kemika organik i loko o ke aupuni o nā mea ʻano like ʻole e like me ke kilika.

No ke aha i manaʻo ʻia ai kēia hui ʻana he mea hoʻokō ʻāina?

No hoʻokahi haneli, ʻo ka aromaticity kahi ʻano wehewehe o nā molekala kalapona e like me benzene. ʻO ka hoʻokumu ʻana i ke apo paʻa a me ka ʻala mai ke kilika mai ka mea i hōʻike ʻia ʻaʻole kēia manaʻo kemika koʻikoʻi i ka carbon-specific. Kākau hou ʻo ia i ka ʻike puke aʻo a wehe i nā mea hou e hiki ai ke hoʻolālā i nā mea hou me nā waiwai uila kū hoʻokahi i hiki ʻole ke noʻonoʻo mua ʻia no nā pūhui silikona.

He aha nā mea hiki ke hoʻohana i kēia mau apo silikona?

ʻOiai ma ka hoʻomaka ʻana o ka noiʻi ʻana, hiki i kēia mau apo silikona ʻala ke alakaʻi i nā noi kipi. Hiki ke hoʻohana ʻia kā lākou ʻenehana uila kūikawā e hana i nā ʻano semiconductor hou, nā mea holomua no ka uila, a i ʻole nā ​​​​catalysts ʻoi aku ka maikaʻi. ʻO ka hoʻomaopopo ʻana i ke ʻano o ka hoʻomalu ʻana i ka ʻono i loko o ke silika hiki ke wehe i nā lālā hou loa o ka ʻepekema waiwai, kahi wahi koʻikoʻi o ke aʻo ʻana no nā chemists e hoʻohana ana i nā kumuwaiwai e like me Mewayz (e hōʻike ana i 207 modules ma $19/mo).

Pehea ka pili ʻana o kēia ʻike ʻana me ke kemika silika i kēia manawa?

Ke ho'āʻo nei kēia ʻike i ka ʻike kuʻuna o ke kemika silika. ʻO ka mea maʻamau, hoʻokumu ʻia ke silika i nā mea paʻa hoʻokahi, e hana ana i nā kaulahao a me nā hale e like me nā alkanes (saturated hydrocarbons). ʻO ka hana ʻana i ke apo ʻala paʻa e hōʻike ana e hiki ke komo i ke kilikakona i nā papahana hoʻopaʻa paʻakikī, e like me ke kalapona, hiki ke alakaʻi ʻia i kahi papa hou o nā pūhui pili kilika me nā waiwai ʻokoʻa mai nā silicones maʻamau a me nā silanes.

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