REVIEW JURNAL

Judul The Influence of Antenna and Anchoring Moieties on the

Improvement of Photoelectronic Properties in Zn(II)-Porphyrin-TiO2
as Potential Dye-Sentisized Solar Cells
Jurnal Royal Society Chemistry
Volume & Accepted Maanuscript. DOI 10.1039/C8CP06988C.
halaman
Tahun 2019
Penulis Ricardo Pino-Rios* and Gloria Cárdenas-Jirón*
Rodrigo Urzúa-Leiva,
Tgl 22/04/2019

Tujuan The purpose of the present work is double. On one hand, we wish to show
that the photoelectronic properties of the spider-shaped-porphyrin could
be improved by the bonding in meso positions of the electron donor and
electron acceptor moieties used by Xie et al. On the other hand, to
demonstrate that the application of a protocol of computational calculation
in a systematic way can be very useful for the rational design of porphyrins
with potential application in dye-sensitized solar cells.

Dalam penelitian ini, terdapat 2 tujuan. Pertama,ingin menunjukkan bahwa

sifat photoelectronic dari spider-shaped-porphyrin dapat ditingkatkan
dengan ikatan donor elektron pada posisi meso dan pada bagian akseptor
elektron. Selain itu, untuk menunjukkan bahwa penerapan protokol
perhitungan komputasi secara sistematis dapat sangat berguna untuk
mendesain porfirin secara rasional dan berpotensi digunakan dalam aplikasi
dye-sensitized solar cells
Subjek porphyrins (P4 spider-shaped derivatives)
Penelitian
Metode Using density functional theory (DFT) (B3LYP/6-31G*) and time-
Penelitian dependent DFT (M06/6-31G*)
Langkah 1. Full molecular geometry optimizations for the ground states
Penelitian reported and derivative compounds were performed at the
B3LYP/6-31G level of theory in the gas phase, with no
pseudopotentials being used.
2. Vibrational frequency calculations were performed at the same level
of theory to effectively obtain a true-minimum of the potential
energy surface (PES).
3. Molecular orbitals and HOMO-LUMO energy gap were obtained
using the aforementioned level of theory.
4. the excited states and the electronic absorption spectra were
obtained in the framework of time-dependent density functional
theory (TDDFT) in the solution phase
 5. The theoretical electronic spectra were obtained by Franck-Condon
type singlet-singlet vertical transitions using 80 excited states for
every molecular system.
6. The solvent effect (toluene) was taken into account in the
absorption spectra using the polarizable continuum model (PCM)
with a dielectric constant (ε) of 2.37
7. The level of theory used for the calculation of the excited states was
M06/6-31G
8. All the calculations for the ground and excited states were
performed using the Gaussian09 computational package
9. Density difference plots were made using Multiwfn in conjunction
with Chemcraft software at the B3LYP/6-31G* level of theory.
Hasil Penelitian
Kekuatan
Penelitian
Kelemahan
Penelitian
Kesimpulan 1. Several Zn(II)-porphyrin derivatives from the so-called "spider"-
shaped dyes were modelled and studied systematically using DFT
and TD-DFT theoretical calculations.
2. For the P8 dye the results showed that the reduction of the long
dodecyloxy chains to methoxy moieties does not dramatically affect
the absorption bands.
3. The systematic removal of the so-called "legs" showed an
incremental blue-shift from P8 to P2, as a result of the
destabilization effect of the legs in the frontier Mos.
4. Following the push-pull strategy to improve this type of porphyrins,
our results indicated that the selected triphenylamine push group
induces a remarkable improvement in the absorption bands of all P4
spider-shaped derivatives.
5. The adsorption of the P4 spider-shaped derivatives onto a TiO2-
anatase surface model through the carboxylic acid group showed
that the rational design is successfully applied to systematic studies
of porphyrins improved by push-pull strategies within the context of
their potential application in dye-sensitized solar cells.

Noted:
1. Metode DFT yang digunakan dalam penelitian ini menggunakan fungsional hybrid
(B3LYP). Fungsional hybrid (B3LYP) adalah metode yang mengkombinasikan perkiraan
Hartree - Fock dengan pertukaran energi dan perkiraan DFT dengan pertukaran energi,
semuanya dikombinasikan dalam fungsional yang meliputi korelasi elektron. Fungsional
tersebut digunakan karena senyawa yang diprediksi sifat dan struktur elektroniknya
merupakan senyawa organik yang mengandung logam.
2. set basis yang digunakan adalah 6-31G* karena berdasarkan literatur yang ada, set basis ini telah
sukses dalam memodelkan senyawa organik yang membentuk kompleks dengan logam.
3. Notasi 6-31G* menandakan di dalam set basis ini terdapat enam fungsi Gaussian yang
mewakili orbital ini, tiga fungsi Gaussian untuk orbital elektron valensi bagian yang
terkontraksi, dan satu untuk bagian yang berdifusi. Notasi (*) menunjukkan fungsi
polarisasi pada atom non hidrogen (dalam senyawa di atas adalah atom C, N dan O).
 Abstrak
The development of building integrated photovoltaic (BIPV) technology and its
implementation in construction of the building envelop provide aesthetical, economical and
technical solutions toward the zero-energy building. In this perspective dye-sensitized solar cells
(DSSCs), which can be obtained in transparent form and with tunable different colors, offer not
only an alternative to the traditional silicon solar cells to be applied in particular to decorative
effects on windows and glass integrated façades, but also to indoor structures (and furnishings)
in order to recapture the energy spent for the inner lighting, thanks to their peculiar ability of
operating in diffuse light condition.
Pengembangan teknologi photovoltaic (BIPV) bangunan terintegrasi dan implementasinya
dalam konstruksi selubung bangunan memberikan solusi estetika, ekonomis dan teknis menuju
bangunan tanpa energi. Dalam perspektif ini sel surya peka-warna (DSSCs), yang dapat
diperoleh dalam bentuk transparan dan dengan warna yang berbeda, tidak hanya menawarkan
alternatif sel surya silikon tradisional untuk diterapkan khususnya pada efek dekoratif pada
jendela dan fasad kaca terintegrasi , tetapi juga untuk struktur dalam ruangan (dan perabotan)
untuk mendapatkan kembali energi yang dihabiskan untuk penerangan bagian dalam, berkat
kemampuan khusus mereka dalam beroperasi dalam kondisi cahaya yang tersebar.
In this context, porphyrin-based molecules have an immense potential as light harvesting
component of dye-sensitized nanocrystalline TiO2 solar cells, reaching now efficiencies up to
about 13%. However the multistep synthesis of the best performing porphyrin dyes, showing a
meso substitution pattern, is characterized by very low overall yields compromising their
possible applicative development for instance in large photovoltaic (PV) glass modules in
competition with the actual commercial PV glass modules based on CuInGaSe2 or CdTe thin
voltaic films.
Dalam konteks ini, molekul berbasis porfirin memiliki potensi yang sangat besar sebagai
komponen pemanen cahaya dari sel surya TiO2 nanokristalin peka-warna, yang sekarang
mencapai efisiensi hingga sekitar 13%. Namun sintesis multistep dari pewarna porphyrin
berkinerja terbaik, menunjukkan pola substitusi meso, dicirikan oleh hasil keseluruhan yang
sangat rendah mengkompromikan pengembangan aplikatif yang mungkin mereka misalnya
dalam modul kaca photovoltaic (PV) besar dalam persaingan dengan modul kaca PV komersial
aktual berdasarkan Film volta tipis CuInGaSe2 atau CdTe.
In this review the renewed interest in the role of the b-substituted Zn porphyrins for PV
application, less studied than the meso substituted ones, is highlighted. Indeed they can rely on a
more accessible synthetic procedure since their tetraaryl porphyrinic core can be easily obtained
by a one pot reaction between pyrrole and the appropriate aryl aldehyde. Moreover, their
remarkable light harvesting properties in the visible range as well as their peculiar steric
hindrance, which strongly opposes to the charge recombination process at the
photoanode/dye/electrolyte interface, make this kind of cost-effective porphyrinic dyes more
promising for application in new PV glass modules based on DSSC technology, to be applied
BIPV.
Dalam ulasan ini, minat baru dalam peran porfirin Zn tersubstitusi-b untuk aplikasi PV,
kurang dipelajari daripada yang tersubstitusi meso, disorot. Memang mereka dapat
mengandalkan prosedur sintetik yang lebih mudah diakses karena inti tetraaryl porphyrinic
mereka dapat dengan mudah diperoleh dengan reaksi satu pot antara pirol dan aril aldehida yang
sesuai. Selain itu, sifat pemanenan cahaya yang luar biasa dalam kisaran yang terlihat serta
hambatan sterik khas mereka, yang sangat menentang proses rekombinasi muatan pada
antarmuka photoanode / pewarna / elektrolit, membuat pewarna porfirinik hemat biaya semacam
ini lebih menjanjikan untuk aplikasi di modul kaca PV baru berdasarkan teknologi DSSC, untuk
diterapkan BIPV.
Judul Β-Substitued ZnII porphyrin as dyes for DSSC: A possible approach to
pphotovoltaic windows
Jurnal Elsivier; Coordination Chemistry Reviews
Volume & 338, 153-177
halaman
Tahun 2018
Penulis Gabriele Di Carlo, Alessio Orbelli Biroli, Francesca Tessore, Stefano
Caramori, dan Maddalena Pizzoti
Tgl 19/07/2019

Tujuan
Subjek porphyrins (P4 spider-shaped derivatives)
Penelitian
Metode Using density functional theory (DFT) (B3LYP/6-31G*) and time-
Penelitian dependent DFT (M06/6-31G*)
Langkah 10. Full molecular geometry optimizations for the ground states
Penelitian reported and derivative compounds were performed at the
B3LYP/6-31G level of theory in the gas phase, with no
 pseudopotentials being used.
11. Vibrational frequency calculations were performed at the same level
of theory to effectively obtain a true-minimum of the potential
energy surface (PES).
12. Molecular orbitals and HOMO-LUMO energy gap were obtained
using the aforementioned level of theory.
13. the excited states and the electronic absorption spectra were
obtained in the framework of time-dependent density functional
theory (TDDFT) in the solution phase
14. The theoretical electronic spectra were obtained by Franck-Condon
type singlet-singlet vertical transitions using 80 excited states for
every molecular system.
15. The solvent effect (toluene) was taken into account in the
absorption spectra using the polarizable continuum model (PCM)
with a dielectric constant (ε) of 2.37
16. The level of theory used for the calculation of the excited states was
M06/6-31G
17. All the calculations for the ground and excited states were
performed using the Gaussian09 computational package
18. Density difference plots were made using Multiwfn in conjunction
with Chemcraft software at the B3LYP/6-31G* level of theory.
Hasil Penelitian
Kekuatan
Penelitian
Kelemahan
Penelitian
Kesimpulan 6. Several Zn(II)-porphyrin derivatives from the so-called "spider"-
shaped dyes were modelled and studied systematically using DFT
and TD-DFT theoretical calculations.
7. For the P8 dye the results showed that the reduction of the long
dodecyloxy chains to methoxy moieties does not dramatically affect
the absorption bands.
8. The systematic removal of the so-called "legs" showed an
incremental blue-shift from P8 to P2, as a result of the
destabilization effect of the legs in the frontier Mos.
9. Following the push-pull strategy to improve this type of porphyrins,
our results indicated that the selected triphenylamine push group
induces a remarkable improvement in the absorption bands of all P4
spider-shaped derivatives.
10. The adsorption of the P4 spider-shaped derivatives onto a TiO2-
anatase surface model through the carboxylic acid group showed
that the rational design is successfully applied to systematic studies
of porphyrins improved by push-pull strategies within the context of
their potential application in dye-sensitized solar cells.
Photosynthesis, the natural process through which plants convert sunlight into chemical
energy, represents one of the more relevant photophysical natural processes, where chlorophylls,
containing several porphyrin molecules, play the role of light harvesting antennae. As a
consequence a large interest in metal porphyrins as dyes or in general as antennae was raised, by
virtue of their strong electronic absorption bands at around 500 and beyond 600 nm and their
long lived p⁄ singlet excited states of appropriate LUMO energy, to allow injection of the excited
electron into the TiO2 semiconductor. They have also the advantage of a molecular structure
with many reaction sites, four meso and eight b pyrrolic positions, which can be functionalized,
allowing fine tuning of their

Fotosintesis, proses alami di mana tanaman mengubah sinar matahari menjadi energi
kimia, merupakan salah satu proses alami fotofisika yang lebih relevan, di mana klorofil, yang
mengandung beberapa molekul porfirin, berperan sebagai antena pemanen cahaya. Sebagai
akibatnya, minat yang besar pada logam porfirin sebagai pewarna atau secara umum seperti
antena dinaikkan, berdasarkan pita serapan elektronik mereka yang kuat pada sekitar 500 dan
lebih dari 600 nm dan kondisi hidrolisis LUMO yang sesuai untuk umur panjang, untuk
memungkinkan injeksi elektron tereksitasi ke dalam semikonduktor TiO2. Mereka juga memiliki
keuntungan dari struktur molekul dengan banyak situs reaksi, empat meso dan delapan b pyrrolic
posisi, yang dapat difungsikan, memungkinkan penyetelan yang baik dari sifat elektronik dan
fotofisika mereka.

Until 2010, the energy conversion efficiency for DSSC based on porphyrinic dyes was
much lower than those based on ruthenium complexes, but the development of porphyrinic
push–pull systems with a strong directional HOMO–LUMO transition around 600 nm and the
introduction of bulky substituents into the porphyrinic structure in order to avoid p–p
aggregation on the photoanode, have significantly improved the efficiencies of the DSSCs based
on Zn porphyrin dyes up to 12.3%
Sampai 2010, efisiensi konversi energi untuk DSSC berdasarkan pewarna porfirin jauh
lebih rendah daripada yang berbasis pada kompleks rutenium, tetapi pengembangan sistem
tarikan porfirin dengan transisi HOMO-LUMO arah yang kuat sekitar 600 nm dan pengenalan
substituen besar ke dalam struktur porfirinik untuk menghindari agregasi p-p pada photoanode,
telah secara signifikan meningkatkan efisiensi DSSCs berdasarkan Zn porphyrin, hingga 12,3%
On the basis of these latter results, 5,15 meso disubstituted push–pull Zn II porphyrins,
characterized by a strong and directional charge transfer process along the push–pull system,
were considered as the best porphyrinic structures allowing high DSSC efficiencies.
Atas dasar hasil yang terakhir ini, 5,15 meso disubstitusi push-pull Zn II porphyrins,
dicirikan oleh proses transfer charge yang kuat dan terarah sepanjang sistem push-pull, dianggap
sebagai struktur porfirin terbaik yang memungkinkan efisiensi DSSC tinggi.
However their syntheses, which require multiple steps, are characterized by very low
overall yields [25–29], (9–32% starting from porphyrin core and depending on complexity of the
structure) making difficult to imagine a possible applicative development for instance in PV
glass modules to be integrated in building façades or in ‘‘smart” windows.
Namun sintesis mereka, yang memerlukan beberapa langkah, dicirikan oleh hasil
keseluruhan yang sangat rendah [25-29], (9–32% dimulai dari inti porfirin dan tergantung pada
kompleksitas struktur) membuat sulit untuk membayangkan kemungkinan pengembangan
aplikasi misalnya di Modul kaca PV akan diintegrasikan dalam membangun fasad atau di jendela
'' pintar '.
 On the other hand, b substituted tetraaryl Zn porphyrins can rely on a symmetric core,
easily obtained by a one pot reaction between pyrrole and the appropriate aryl aldehyde, making
them synthetically less demanding. Moreover, the attachment of an appropriate functional
substituent to the b pyrrolic position, such as a p-ethynyl phenyl system carrying a carboxylic
ending group, II can be now obtained by a rather simple synthetic approach
Di sisi lain, porfirin tetraaryl Zn tersubstitusi dapat bergantung pada inti simetris, mudah
diperoleh dengan reaksi satu pot antara pirol dan aril aldehida yang sesuai, membuatnya secara
sintetis kurang menuntut. Selain itu, perlekatan substituen fungsional yang sesuai dengan posisi
pirolitik, seperti sistem p-etilil fenil yang membawa gugus akhir karboksilat, II sekarang dapat
diperoleh dengan pendekatan sintetik yang agak sederhana.
so that a new class of b substituted porphyrinic dyes could be probably quite suitable for
large scale production necessary for the development of colored PV glass modules based on
DSSC technology. Despite an encouraging efficiency (g) of 7.1% has been attained already in
2007 by the pale green b-substituted tetraaryl II Zn porphyrin.
sehingga kelas baru pewarna porfirin tersubstitusi mungkin cukup cocok untuk produksi
skala besar yang diperlukan untuk pengembangan modul kaca PV berwarna berdasarkan
teknologi DSSC. Meskipun ada efisiensi yang menggembirakan (g) dari 7,1% yang telah dicapai
pada tahun 2007 oleh tetraaryl II Zn-pn tersubstitusi hijau pucat
As discussed later in detail in Section 4, DFT calculations have shown that, comparing
with the reference unsubstituted Zn II tetraarylporphyrin (ZnTPP), the presence of electron
withdrawing groups on the b substituent modulates the absorption spectrum stabilizing the
energies of the LUMO and LUMO+2 orbitals, with an extension of these orbitals onto the b
substituent which implies an increased tendency of electron transfer from the porphyrinic core to
the b substituent and consequently to the TiO2 surface [48].
Sebagaimana dibahas kemudian secara rinci dalam Bagian 4, perhitungan DFT telah
menunjukkan bahwa, dibandingkan dengan referensi tetraarylporphyrin Zn II yang tidak
disubstitusi (ZnTPP), keberadaan gugus penarik elektron pada substituen b memodulasi
spektrum serapan yang menstabilkan energi LUMO dan LUMO + 2 orbital, dengan ekstensi
orbital ini ke substituen b yang menyiratkan kecenderungan peningkatan transfer elektron dari
inti porfirinik ke substituen b dan akibatnya ke permukaan TiO2 [48].
A comparative investigation on tetraaryl b monosubstituted and 5,15 meso push–pull
disubstituted diaryl Zn porphyrins has been carried out by Pizzotti and co-workers [24] in order
to compare II their performances in DSSCs (Fig. 6). Although the HOMO–LUMO energy gap of
the push–pull meso-disubstituted porphyrins is narrower, thus allowing an easier charge transfer
along the push–pull system, the b mono substituted dyes show comparable or even better DSSC
efficiencies.
Sebuah investigasi komparatif pada tetraaryl b monosubstituted dan 5,15 meso diaryl
disubstituted diaryl Zn porphyrins telah dilakukan oleh Pizzotti dan rekan kerja [24] untuk
membandingkan II kinerja mereka dalam DSSCs (Gbr. 6). Meskipun kesenjangan energi
HOMO-LUMO dari porfirin yang disubstitusi terdorong-tarik lebih sempit, sehingga
memungkinkan transfer muatan yang lebih mudah di sepanjang sistem dorong-tarik, pewarna
yang tersubstitusi b mono menunjukkan efisiensi DSSC yang sebanding atau bahkan lebih baik.
This behavior was attributed, in first approximation, to a more facile charge injection into
the photoanode, as suggested by the electron distribution obtained by DFT calculations of a
simple model of a b monosubstituted Zn porphyrinic dye interacting with the TiO2 surface [24].
In agreement with these findings, IPCE spectra of b substituted Zn II porphyrinic dyes show
more intense values over the range 350–650 nm compared to those of meso substituted ones
which produce IPCE spectra with two well separated less intense peaks, strictly corresponding to
B and Q absorption bands of the push–pull system (Fig. 7). II
Perilaku ini dikaitkan, pada pendekatan pertama, ke injeksi muatan yang lebih mudah ke
photoanode, seperti yang disarankan oleh distribusi elektron yang diperoleh dengan perhitungan
DFT dari model sederhana dari pewarna porphyrinic Zn b monosubstituted yang berinteraksi
dengan permukaan TiO2 [24]. Dalam persetujuan dengan penemuan ini, spektra IPCE dari zat
pewarna porfirin Zn II tersubstitusi b menunjukkan nilai yang lebih kuat pada kisaran 350-650
nm dibandingkan dengan yang dari meso yang tersubstitusi yang menghasilkan spektrum IPCE
dengan dua puncak yang tidak terlalu kuat yang dipisahkan dengan baik, sangat sesuai dengan B
dan Pita serapan Q pada sistem dorong-tarik (Gbr. 7). II