Bridging the Green Gap: Metal–Organic Framework Heteromultilayers Assembled from Porphyrinic Linkers Identified by Using Computational Screening

Article abstract of DOI:10.1002/chem.201901585

In organic photovoltaics, porphyrins (PPs) are among the most promising compounds owing to their large absorption cross-section, wide spectral range, and stability. Nevertheless, a precise adjustment of absorption band positions to reach a full coverage of the so-called green gap has not been achieved yet. We demonstrate that a tuning of the PP Q- and Soret bands can be carried out by using a computational approach for which substitution patterns are optimized in silico. The most promising candidate structures were then synthesized. The experimental UV/Vis data for the solvated compounds were in excellent agreement with the theoretical predictions. By attaching further functionalities, which allow the use of PP chromophores as linkers for the assembly of metal-organic frameworks (MOFs), we were able to exploit packing effects resulting in pronounced redshifts, which allowed further optimization of the photophysical properties of PP assemblies. Finally, we use a layer-by-layer method to assemble the PP linkers into surface-mounted MOFs (SURMOFs), thus obtaining high optical quality, homogeneous and crystalline multilayer films. Experimental results are in full accord with the calculations, demonstrating the huge potential of computational screening methods in tailoring MOF and SURMOF photophysical properties.

Full text of DOI:10.1002/chem.201901585

A Journal of
Accepted Article
Title: Bridging the green gap: MOF hetero-multilayers assembled from
porphyrinic linkers identified using computational screening
Authors: Christof Wöll, Ritesh Haldar, Kamal Batra, Stefan Marschner,
Agnieszka Kuc, Stefan Zahn, Roland Fischer, Stefan Bräse,
and Thomas Heine
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To be cited as: Chem. Eur. J. 10.1002/chem.201901585
Link to VoR: http://dx.doi.org/10.1002/chem.201901585
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Bridging the green gap: MOF hetero-multilayers assembled from
porphyrinic linkers identified using computational screening
Ritesh Haldar,±[a] Kamal Batra,±[b] Stefan Michael Marschner,[c] Agnieszka B. Kuc,[d] Stefan Zahn,[e]
Roland A Fischer,[f] Stefan Bräse,[c,g] Thomas Heine,*[b,d] Christof Wöll*[a]
Abstract: In organic photovoltaics, porphyrins (PPs) are among the
most promising compounds owing to their large absorption cross
section, wide spectral range, and stability. Nevertheless, a precise
adjustment of absorption band positions to reach a full coverage of
the so-called green gap has not been achieved yet. We demonstrate
that a tuning of the PP Q- and the Soret bands can be done using a
computational approach where substitution patterns are optimized in
silico. The Most promising candidate structures were then
synthesized. The experimental UV/Vis data for the solvated
compounds were in excellent agreement with the theoretical
predictions. By attaching further functionalities, which allow using the
PP chromophores as linkers for the assembly of metal-organic
frameworks (MOFs), we were additionally able to exploit packing
effects resulting in pronounced red shifts, which allowed to further
optimizing the photophysical properties of PP assemblies. Finally,
we use a layer-by-layer method to assemble the PP linkers into
surface-mounted MOFs (SURMOFs), thus obtaining high optical
quality, homogeneous and crystalline multilayer films. Experimental
results are in full accord with the calculations, demonstrating a huge
potential of computational screening methods in the tailoring of MOF
and SURMOF photophysical properties.
While presently the highest conversion efficiencies are achieved
with inorganic (Si, Ge)[1] and hybrid (Grätzel-cell, perovskites)[2]
semi-conductor based photovoltaic (PV) devices, organic
materials are an interesting alternative with advantages in more
specific applications.[3] Main obstacles in this area are efficiency
and stability issues. Progress in this field is only gradual, and the
search for organic molecules suited as an active PV material is
to a large extent still dominated by empirical approaches.[3,4] Use
of computer-based screening methods is hampered by the fact
that the characteristics of most organic PV (OPV) materials are
strongly impacted by intermolecular interactions.[5] and, for
disordered systems, many configurations have to be samples to
make reliable predictions.[6]
Major progress has thus to be expected when employing
crystalline systems with exactly known structures.[7] In such
cases, periodic boundary conditions can be applied, which
allows for a thorough theoretical analysis utilizing the solid state
analysis toolbox.[6] The OPV device characteristics can then be
predicted on the basis of first-principles electronic structure
calculations carried out both for single molecules as well as for
the condensed phases of these organic semiconductors. In the
latter case, the precise arrangement of the functional molecules
in the crystalline state is taken fully in account. In addition to a
reliable theoretical analysis with high predictive power, for
crystalline systems additional effects may be employed, e.g. the
emergence of band dispersion favoring large charge carrier
mobilities and the formation of indirect band gaps.[8] Indirect
band gaps are beneficial in photovoltaics since they favor a fast
and highly efficient charge separation and thus charge carrier
recombination is strongly suppressed.
[a]
Dr. R. Haldar, Prof. Dr. C. Wöll
Karlsruhe Institute of Technology (KIT)
Institute of Functional Interfaces (IFG)
Hermann-von-Helmholtz Platz 1
76344 Eggenstein-Leopoldshafen (Germany)
E-mail: christof.woell@kit.edu
K. Batra, Prof. Dr. T. Heine
Theoretische Chemie, Technische Universität Dresden
Bergstraße 66c, König-Bau
01062 Dresden (Germany)
E-mail: thomas.heine@tu-dresden.de
S. M. Marschner, Prof. Dr. S. Bräse
Karlsruhe Institute of Technology (KIT)
Institute of Organic Chemistry (IOC)
Fritz Haber Weg 6
[b]
[c]
Here, we demonstrate an approach based on assembly of
multi-functionalized PP linkers into thin films of MOFs.[9] PPs are
76351 Karlsruhe (Germany)
[d]
[e]
[f]
Dr. A. B. Kuc, Prof. Dr. T. Heine
Helmholtz-Zentrum Dresden-Rossendorf
Permoserstraße 15
04318 Leipzig (Germany)
Dr. S. Zahn
Leibniz Institute für Oberfläschenmodifizierung e.V.
Permoserstraße 15
04318 Leipzig (Germany)
Prof. Dr. R. A. Fischer
Technical University of Munich
Lichtenberg Straße 4
a
particular promising class of organic compounds for
investigating the beneficial effect of a regular arrangement of
photoactive molecules with regard to light harvesting.[10] PPs
form a very rich class (> 100,000 compounds known)[11,12] which
are also common in nature. In plants, PPs like chlorophyll
transform solar energy into chemical energy. Since PPs are
among the best-performing organic compounds regarding
photon absorption, charge separation, and stability,[12] numerous
previous works have been carried out with the aim to prepare
well-defined, thin films of PP aggregates deposited on
conducting and transparent substrates.[13] The approaches
employed previously include vapour-phase deposition of PP
molecules, a rather sophisticated method, or self-assembly from
appropriate solutions. The latter strategy has been rather
successful, but the resulting systems do not exhibit a high
degree of ordering, thus largely excluding the formation of band-
structure effects. In addition, the different types of molecular
85748 Garching (Germany)
Prof. Dr. S. Bräse
[g]
Karlsruhe Institute of Technology (KIT)
Institute of Toxicology and Genetics (ITG)
Hermann-von-Helmholtz Platz 1
76344 Eggenstein-Leopoldshafen (Germany)
± Authors contributed equally.
Supporting information for this article is given via a link at the end of
the document.
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Figure 1. a) Typical spectrum of a porphyrin. Blue lines in the Lewis structure highlight the π-electrons on which a 18π cyclic polyene model is reasonable;
b) Comparison of the frontier orbitals obtained from DFT calculations of porphyrin and the 18π cyclic polyene model.
packing in the amorphous films make more precise predictions
of absorption properties difficult.
(sTD-DFT) was applied (see SI for computational details). As
expected, functionalization is found to be a suitable means for
both Q band intensity enhancement and tuning of absorption
band positions. For example,  substitution by Br as well as
meso positioned phenyl group substitution creates a large red
shifts of Q bands by >50 nm in comparison to 1-H (see Table
S2). Additionally, the absorption of the Q bands is significantly
enhanced (Figure S3).
The typical absorption spectrum of a PP chromophore
consists of a sharp, high-intensity Soret band, which is typically
located in the UV region, and four Q bands located in the visible
range (Figure 1a). In principle all transitions of the frontier
orbitals are symmetry-allowed. However, as the frontier orbitals
are nearly degenerate, the electronic structure can be
approximated by a 18 π cyclic polyene model, as suggested by
Gouterman,[14] where two transitions are allowed between the
degenerated frontier orbitals (Δk=1), while two are forbidden
(Δk=9) (Figure 1b). Detailed quantum chemical studies confirm
Gouterman’s conclusions and explain the typical absorption
spectra of PPs in detail.[15] Tuning the energy levels of HOMO-1,
HOMO, LUMO and LUMO+1 strongly affects the absorption
intensity of the characteristic absorption bands of porphyrins.
The higher the energy gap between HOMO-1 and HOMO as
well as LUMO and LUMO+1, the stronger will be the absorption
intensity of the Q-bands. While this allows the rational design of
PP molecules, the prognostication of absorption spectra for PP-
based SURMOFs remains difficult. This is mainly due to the fact
that the bulk structure is not known a priori, and changes of
absorption intensity and band positions resulting from
intermolecular interactions are thus difficult to predict.
On the basis of this computational screening, three PPs
Here, we circumvent the problem of structure prediction
for the condensed phase by focusing on porphyrinic dicarboxylic
acids which can be used as ditopic linkers to assemble PP-
MOFs. In order to identify a small set of chromophoric MOF
Figure 2. a) Three selected PP linkers; (b) TD-DFT predicted (left) and
experimental (right) UV-Vis spectra of the linkers. Experimental spectra
were recorded for 20 M ethanolic solution of the linkers at RT.
linkers to cover the green gap we first carried out
a
computational screening of a library containing 14 PP structures
(Figure S1). This library was generated by functionalization of
two of the phenyl rings at the meso positions with carboxylate
groups to produce ditopic MOF linkers. In the first group of PP
derivatives, the H atoms at the β positions are substituted by
halides and methyl groups (1-X group, X = F, Cl, Br, CH3), and
in the second group the two phenyl rings that do not serve as
linking groups are substituted. The library contains substitution
groups which can modulate PP ring planarity (e.g. substitution at
-position by bulky Br atoms), and also electron density (electron
donating /pulling).
(Figure 2a) have been selected for synthesis (see experimental
section in supporting information) and validation of the
theoretical predictions. Selection criteria were the enhancement
of Q-band intensity and the tuning of band position. These
selected three PPs exhibit important differences: i) the presence
of electron withdrawing functional groups (fluorinated phenyl), ii)
- conjugation of the substituent (phenyl group or acetylene
group), and iii) planarity of the porphyrin core (twisted octabromo
porphyrin). The experimental methods developed for organic
synthesis of the multi-substituted porphyrins were successful.
In order to obtain theoretical predictions with sufficient
reliability, simplified time-dependent density-functional theory
The required A2B2-type porphyrins were assembled in
a
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modular fashion starting from dipyrromethene building blocks
and functional aldehydes. Subsequent cross-coupling reactions
led to the designed porphyrins (see experimental section in
supporting information). Figure 2b, shows the predicted (left)
and experimental (right) UV-Vis spectra of 1-Br, 5 and 10.
Generally, a good agreement is seen between the TD-DFT gas-
phase predictions and the experimental results (solvated). Note,
that the agreement is not expected to be quantitative since
solvatochromic shift affect the experimental absorption
spectra.[16] In these synthesized PPs, apart from the Q-bands in
near-IR region, also the Soret band shifts to visible range, in
comparison to the 1-H.
excellent agreement with the prediction. These observations
confirm the expectation that irrespective of the type of group
attached at meso or β position to the PPs, the unit cell
parameters of the resulting MOF structures remain unchanged.
(Figure 3, for details, see supplementary information). Figures
3b-d show the DFTB optimized atomistic structures of 1-Br, 5
and 10. In 10, fluorination of the linkers creates significant
electrostatic repulsion, so the inter-linker distance is maximized
when the PPs are untwisted. This maintains the overall P4
symmetry in 10 with a distance between the PP units of 6.3 Å. In
For applications, the assembly of PP dyes into thin films of
high optical quality is crucial. Therefore, in a final step, the
selected PP linkers were assembled into SURMOF-2 thin films
containing optically silent Zn2 paddle wheel units, following the
spin-coated variant of the layer-by-layer (lbl) liquid phase epitaxy
method.[17] The SURMOF-2 structure consists of Zn2-paddle-
wheel (PW) type secondary building units (SBUs) tethered with
ditopic linkers to yield two-dimensional planes stacked along the
(010) crystallographic direction (Figure 3).[18] Note that the
framework of SURMOF-2 has P4 symmetry, and the lattice
constant only depends on the length of the PP linkers (i.e. the
Figure 4. Experimental UV-Vis comparison spectra of the synthesized
PP linkers (solid line) and their corresponding fabricated SURMOF-2
structures (broken line); a) 1-Br, b) 5 and c) 10. Note that the molecular
spectra are recorded in ethanol at RT.
contrast, the longer linkers in 5′ interact strongly, causing a tilting
of 32° and reducing the distance between the PP planes to 3.3 Å.
these of the solvated linker molecules 1-Br, 5 and 10. In 1-Br,
Figure 4 compares the UV-Vis spectra of 1-Br, 5 and 10
with the distorted basal planes of the linker (1-Br) prevent
periodicity along the PP stacks (along (010)). Consequently, the
bands are not shifted compared to those of the solvated 1-Br,
but significantly broadened (Figure 4a). However, the
Figure 3. a) Simulated XRD pattern of 1-Br, and experimental out-of-
plane XRD patterns of 1-Br, 5 and 10; calculated atomistic structures of
b) 1-Br, c) 5 and d) 10, view along [010] direction.
experimental data reveal that crystallization of
5 in the
distance between the two carboxylic acid groups), while the
addition of side-groups to the PPs are not expected to create
changes of the SURMOF unit cell.
In all three cases, SURMOF-2 structures, labelled as 1-Br,
5 and 10, exhibit well-defined out-of-plane XRD patterns
(Figure 3a). The position of the diffraction peaks are almost
identical, yielding unit cell dimensions with a = b = 2.3 nm, in
SURMOF-2 structure causes a significant red shift of all bands
in 5 (Figure 4b). Notably, this red shift affects both the Soret and
the Q bands. In addition, all bands are substantially broadened.
The spectra of 10 and 10 are very similar, indicating negligible
interaction between the PP linkers (also in line with the predicted
structure) (Figure 4c).
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To rationalize the experimental UV-Vis spectra recorded
for the PP-SURMOFs, we have calculated the band structures of
1-Br, 5 and 10 (for details, see supporting information), which
are shown in Figure 5(a-c). The band structure of 1-Br reflects
the idealized structure and therefore is not directly suitable to
interpret the UV-Vis spectrum (Figure 5a). For 5, we observe
significant band dispersion along the Z direction of the Brillouin
zone (see Figure 5b, 5d), which is responsible, both for the red
shift of the absorption bands, as well as for the charge carrier
mobility along the PP stacks (along (010)). We observe an
indirect band gap of ~ 200 meV, which is substantially larger
than that (5 meV) reported in previous work for a different PP-
SURMOF-2 structure.[19] For 10, no band dispersion is observed,
confirming the hypothesis that the linker molecules 10 do not
interact in the SURMOF-2 structure (Figure 5c). As a result, the
UV-Vis data for the corresponding SURMOF-2 film mainly show
the molecular features. Due to the lack of band dispersion, no
ballistic transport is possible for such structure. While for the 1-
Br′ and 10′ no substantial aggregation-induced shifts of the
absorption band positions were observed, a broadening of the
absorption bands is evident. This is a beneficial effect, and
together the three PP-linkers allow covering the full visible
spectrum ranging from violet to near-IR. Inspired by such broad
absorption, we have fabricated
a multilayer SURMOF-2
structure by employing heteroepitaxy.[20] Layers of 1-Br, 5 and
10 were sequentially deposited on top of each other to make a
crystalline thin film with a broad absorption ranging UV-to-NIR,
as shown in Figure 5e. Such straightforward fabrication method,
combining all the potential photon absorbing dyes as a thin film
is a promising strategy towards further improvement of OPV
materials.
In conclusion, we present here an attractive route to create
OPV absorber layers in the visible regime, covering the entire
range from the violet to the near infrared, including the green
gap. Starting point is a set of candidate structures, in this case,
tetraphenyl porphyrin derivatives with different substitution
patterns. Instead of scheduling a vast amount of structures for
synthesis, we used a computational approach to first select
promising chromophoric MOF linkers from an in-silico library.
Indeed, after synthesis, the three candidates, showed excellent
performance. 1-Br exhibits distorted basal plane that imposes a
significant red shift of both Soret and Q-bands in the free
molecule. The second one (5) has a large aromatic ligand
(extended conjugation), which enhances the Q-band intensity,
but does not affect the position of the Soret band. The third one
(10) is functionalized with strong electrostatically active groups.
Arranging these dyes into a SURMOF-2 structure yields three
different pictures: In 1-Br′, distorted basal planes of the linkers
avoid regular stacking, and while the positions of the absorption
bands of the free linkers are maintained, they are significantly
broadened in the SURMOF structure. In 5′, the strong
intermolecular interactions lead to a red shift and broadening of
all bands. Finally, in 10′, electrostatic repulsion reduces
intermolecular interactions and thus the absorption spectrum of
the corresponding SURMOF is dominated by the molecular
properties of 10.
Figure 5. (a-c) Band structure of 1-Br, 5′ and 10′; (d) brillouin zone; (e) a
schematic illustration of trilayer SURMOF (left) and corresponding UV-
Vis spectrum (right). (The gray filled box = SBU, filled diamond shape =
PP).
MOF, one can realize systems with small inter-chromophore
coupling, which are essentially dominated by features of the
individual molecules. By adjusting the MOF topology together
with chromophore substitution patterns, intermolecular couplings
can be introduced, which allow to invoke band structure effects,
thus increasing charge carrier mobility and allowing of indirect
band gap formation. Finally, the SURMOF approach then
provides the prospect to realize energy funneling via fabrication
of hetero-multilayers or gradient structures.
Experimental Section
Fabrication of SURMOFs: Ethanolic solution of 1 mM zinc acetate and 20
μM porphyrin linker solutions (in Ethanol) were sequentially deposited
onto the substrates using spin coating method in a layer-by-layer fashion.
After the metal or linker coating, the samples were rinsed with ethanol to
remove unreacted metal/linker or by-products from the surface. For metal
and linker both, the spin coating time is fixed as 10 s with rpm of 2000.
The thickness of the samples was controlled by the number of deposition
cycles. In a similar fashion, multilayer SURMOF-2 was fabricated. Each
of the PP linkers (1-Br, 5 and 10) were deposited for 25 cycles. Details
Altogether our results reveal that the strategy to prepare
chromophoric assemblies via
a SURMOF-based approach
carries a huge potential. Depending on the stacking within the
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on synthesis of molecular compounds and computational details are
given in the SI.
Zhou, Chem. Sci. 2015, 6, 3926-3930; e) M. V. Peters, R. Goddard, S.
Hecht, J. Org. Chem. 2006, 71, 7846-7849; f)
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116,000 possible structures.
Financial support by Deutsche Forschungsgemeinschaft within the
priority program COORNETs (SPP 1928) is gratefully acknowledged. ZIH
Dresden is thanked for providing high-performance computing resources.
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Keywords: Porphyrin absorption • Theoretical prediction •
Green-gap • Surface anchored MOF • Multi-heteroepitaxy
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10.1002/chem.201901585
Chemistry - A European Journal
COMMUNICATION
COMMUNICATION
In-silico prediction, design
and fabrication of ultraviolet
to near IR-absorbing
porphyrin-based metal-
organic thin films.
Ritesh Haldar,±[a] Kamal
Batra,±[b] Stefan Michael
Marschner,[c] Agnieszka B.
Kuc,[d] Stefan Zahn,[e] Roland A
Fischer,[f] Stefan Bräse,[c,g]
Thomas Heine,*[b,d] Christof
Wöll*[a]
Page No. – Page No.
Title
This article is protected by copyright. All rights reserved.